Use of lactones as odor masking agents

ABSTRACT

Suggested is a method for masking odoriferous incorrect notes in oleochemical preparations, by adding to said compositions specific lactones.

FIELD OF INVENTION

The invention is in the field of oleochemical products and relates tothe use of specific lactones for odour improvement.

STATE OF THE ART

Oleochemical raw materials, such as fats and oils, and derivativesthereof of the first and second order are important starting materialsfor producing both laundry detergents, dishwashing detergents andcleaners, but also cosmetic products. The triglycerides and the fattyacid esters obtained therefrom by transesterification serve for exampleas oil bodies, the derivatives produced by saponification orhydrogenation giving anionic and nonionic surfactants, such as e.g.soaps, fatty alcohol sulphates, fatty alcohol ether sulphates or fattyalcohol polyglycol ethers. A common feature of all of these substancesis that they have a typical greasy odour which, upon prolonged storage,moreover develops further unpleasant notes. Reasons for this are,alongside short-chain free fatty acids which are released bysaponification of the triglycerides, in particular aldehydes and othersubstances which are formed by oxidation. As a rule, the odour qualityof the oleochemical substances is inadequate in order to use themdirectly in the various end products.

One method of solving this problem consists in subjecting batches thatare not perfect in terms of odour to a post-treatment, so-calleddeodorization. Here, the raw materials are treated with hot steam,whereupon the odour carriers are distilled off to a large extent.However, the process is associated with a high input of energy.Particularly when it is a question of processing fats and oils that areas cost effective as possible, which by their very nature have thehighest proportion of said undesired odour carriers, this measure is ineconomical terms naturally counterproductive.

In many cases, it is also possible to confine the unpleasant odour byadding an encapsulation agent, as is described for example in WO 2009131748 A1 (BELLE AIR). However, this measure can also be barely realisedfrom an economical point of view.

From the state of the art compositions, in particular cosmeticpreparations are known comprising one or two C₈-C₁₂ alkyllactones (WO2003 070871 A1, US 2006 0207037 A1, WO 2004 009750 A1, WO 19960 04940A1, US 2002 0197287 A1). None of these references, however, disclose theuse of said lactones for masking unpleasant odours.

The most common alternative hitherto has consisted in adding fragrancesto the raw materials that are not perfect in terms of odour—or to theend products confectioned therewith-, said fragrances concealing(masking) the unpleasant odour or combining with it in such a way that anew odour is formed which is less unpleasant. This process too iscomplex and expensive since hitherto considerable amounts of suchmasking substances have always been required.

The object of the present invention therefore consisted in providing newactive ingredients which are able, even in very small concentrations, tocounteract the unpleasant scent notes arising in oleochemical rawmaterials and in the end products produced therewith, such as, forexample, greasy or rancid odour, i.e. to conceal them or combine withthem such that a new pleasant, for example sweet, creamy or aromaticodour is formed.

DESCRIPTION OF THE INVENTION

The invention provides a method for masking odoriferous incorrect notesin oleochemical preparations by adding lactones of the formula (Ia) or(Ib)

in which R¹ is a linear or branched, saturated or unsaturated,optionally hydroxy-substituted hydrocarbon radical having 2 to 22 carbonatoms and 0 or 1 to 3 double bonds and n is the number 1 or 2,

Surprisingly, it has been found that the lactones of the formula (I),even in small amounts, are able not only to mask unpleasant odours in alarge number of oleochemical formulations which have in particulargreasy or rancid notes, but to even intensify pleasant odour notes andto bring them to the fore.

Lactones

The alkyl lactones of the present invention are known substances whichcan be obtained by the relevant processes of organic chemistry. A simplemethod for producing 5-membered γ-lactones consists in evaporatingaqueous solutions of corresponding hydroxycarboxylic acids. Anothermethod of preparing lactones is the Baeyer-Villinger oxidation, duringwhich cyclic ketones are oxidized with peroxycarboxylic acids with ringexpansion.

In the context of the invention, the lactones that are particularlyreadily suitable for improving the odour note of oleochemicalcompositions are those in which, in formula (I), R¹ is linear alkylradicals having 2 to 14 and in particular 6 to 12 carbon atoms.

The lactones here serve specifically for the masking of odour noteswhich are caused by free fatty acids, aldehydes, and oxidation productsof fats and oils in oleochemical products.

In the context of the present invention, the lactones can be used in anydesired products where it is a case of masking unpleasant odour notesthat are caused primarily by fatty derivatives, and/or of replacing themby pleasant odour perceptions. Typical examples of product groups inwhich the lactones can be used are, for example, soap bases, laundrydetergents, dishwashing detergents and cleaners, and also cosmeticpreparations. Preferably, the lactones are used in amounts of from 0.01to 1% by weight, in particular 0.02 to 0.5% by weight and particularlypreferably 0.05 to 0.1% by weight—based on the preparations.

Laundry Detergents, Dishwashing Detergents and Cleaners

The invention further provides laundry detergents, dishwashingdetergents and cleaners at least four lactones selected from the groupconsisting of γ-hexalactone, γ-heptalactone, γ-octalactone,γ-nonalactone, γ-decalactone, γ-undecalactone, γ-dodecalactone,δ-hexalactone, δ-heptalactone, δ-octalactone, δ-nonalactone,δ-decalactone, δ-undecalactone, δ-dodecalactone, and mixtures thereof,where the use concentration of the lactone or of the lactones is usuallyin the range from 0.01 to 1% by weight, preferably 0.1 to 0.5% byweight—based on the preparations.

The laundry detergents, dishwashing detergents and cleaners arepreferably in liquid form and can have further standard commercialconstituents, such as, for example, surfactants, builders, bleaches,bleach activators, thickeners, enzymes, electrolytes, pH regulators,dyes and fragrances, foam inhibitors, antiredeposition agents, opticalbrighteners, greying inhibitors, anticrease agents, antimicrobial activeingredients, preservatives, antioxidants, antistats, UV adsorbers, heavymetal complexing agents and the like. These auxiliaries are described inmore detail below:

Surfactants

Surfactants that can be used to produce the laundry detergents orcleaners are, besides the nonionic surfactants, also anionic, cationic,amphoteric and/or nonionic surfactants and branched alkyl sulphates.

Nonionic surfactants used are preferably alkoxylated, advantageouslyethoxylated, in particular primary alcohols having preferably 8 to 18carbon atoms and on average 1 to 12 mol of ethylene oxide (EO) per moleof alcohol, in which the alcohol radical can be linear or preferably2-methyl-branched, and/or can contain linear and methyl-branchedradicals in a mixture, as are customarily present in oxo alcoholradicals. In particular, however, preference is given to alcoholethoxylates with linear radicals from alcohols of native origin having12 to 18 carbon atoms, for example from coconut, palm, tallow fatty oroleyl alcohol, and on average 2 to 8 EO per mole of alcohol. Thepreferred ethoxylated alcohols include, for example, C12-14-alcoholswith 3 EO, 4 EO or 7 EO, C9-11-alcohol with 7 EO, C13-15-alcohols with 3EO, 5 EO, 7 EO or 8 EO, C12-18-alcohols with 3 EO, 5 EO or 7 EO andmixtures of these, such as mixtures of C12-14-alcohol with 3 EO andC12-18-alcohol with 7 EO. The stated degrees of ethoxylation arestatistical average values which can be an integer or a fraction for aspecific product. Preferred alcohol ethoxylates have a narrowedhomologue distribution (narrow range ethoxylates, NRE). In addition tothese nonionic surfactants, fatty alcohols with more than 12 EO can alsobe used. Examples thereof are tallow fatty alcohol with 14 EO, 25 EO, 30EO or 40 EO. Nonionic surfactants which contain EO and PO groupstogether in the molecule can also be used according to the invention. Inthis connection it is possible to use block copolymers with EO-PO blockunits or PO-EO block units, but also EOPO-EO copolymers and PO-EO-POcopolymers. It is of course also possible to use mixed alkoxylatednonionic surfactants in which EO and PO units are not distributedblockwise, but randomly. Such products are obtainable as a result of thesimultaneous action of ethylene oxide and propylene oxide on fattyalcohols.

A further class of nonionic surfactants which can be used advantageouslyfor producing laundry detergents or cleaners are the alkylpolyglycosides (APG). Alkyl polyglycosides that can be used satisfy thegeneral formula RO(G)Z, in which R is a linear or branched, inparticular 2-methyl-branched, saturated or unsaturated, aliphaticradical having 8 to 22, preferably 12 to 18, carbon atoms, and G is thesymbol which stands for a glycose unit having 5 or 6 carbon atoms,preferably glucose. The degree of glucosidation z here is between 1.0and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1and 1.4.

Nonionic surfactants of the amine oxide type, for exampleN-cocoalkyl-N,N-dimethylamine oxide andN-tallow-alkyl-N,N-dihydroxyethylamine oxide, and the fatty acidalkanolamides may also be suitable for producing the detergents orcleaners. The amount of these nonionic surfactants is preferably notmore than that of the ethoxylated fatty alcohols, in particular not morethan half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of theformulaR—CO—N(R1)-[Z],in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms,R1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbonatoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fattyacid amides are known substances which can usually be obtained byreductive amination of a reducing sugar with ammonia, an alkylamine oran alkanolamine and subsequent acylation with a fatty acid, a fatty acidalkyl ester or a fatty acid chloride. The group of polyhydroxy fattyacid amides also includes compounds of the formula R—CO—N(R1-O—R2)-[Z],in which R is a linear or branched alkyl or alkenyl radical having 7 to12 carbon atoms, R1 is a linear, branched or cyclic alkyl radical or anaryl radical having 2 to 8 carbon atoms, and R2 is a linear, branched orcyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1to 8 carbon atoms, where C1-4-alkyl or phenyl radicals are preferred and[Z] is a linear polyhydroxyalkyl radical whose alkyl chain issubstituted with at least two hydroxyl groups, or alkoxylated,preferably ethoxylated or propoxylated derivatives of this radical. [Z]is preferably obtained by reductive amination of a sugar, for exampleglucose, fructose, maltose, lactose, galactose, mannose or xylose. TheN-alkoxy- or N-aryloxy-substituted compounds can then be converted intothe desired polyhydroxy fatty acid amides by reaction with fatty acidmethyl esters in the presence of an alkoxide as catalyst.

The content of nonionic surfactants in the liquid detergents andcleaners is preferably 5 to 30% by weight, preferably 7 to 20% by weightand in particular 9 to 15% by weight, in each case based on the totalcomposition.

Anionic surfactants used are, for example, those of the sulphonate andsulphate types. Suitable surfactants of the sulphonate type here arepreferably C9-3-alkylbenzenesulphonates, olefinsulphonates, i.e.mixtures of alkene- and hydroxyalkanesulphonates, and alsodisulphonates, as are obtainable for example from C12-8-monoolefins withterminal or internal double bond by sulphonation with gaseous sulphurtrioxide and subsequent alkaline or acidic hydrolysis of thesulphonation products. Also of suitability are alkane sulphonates whichare obtained from C12-8-alkanes, for example by sulphochlorination orsulphoxidation with subsequent hydrolysis or neutralization. Likewise ofsuitability are also the esters of alpha-sulpho fatty acids (estersulphonates), for example the alphasulphonated methyl esters ofhydrogenated coconut, palm kernel or tallow fatty acids.

Also of suitability are sulphonation products of unsaturated fattyacids, for example oleic acid, in small amounts, preferably in amountsnot above about 2 to 3% by weight. In particular, preference is given toalpha-sulpho fatty acid alkyl esters which have an alkyl chain with notmore than 4 carbon atoms in the ester group, for example methyl ester,ethyl ester, propyl ester and butyl ester. With particular advantage,the methyl esters of the alpha-sulpho fatty acids (MES), but also theirsaponified disalts are used.

Further suitable anionic surfactants are fatty acid derivatives of aminoacids, for example of N-methyltaurine (taurides) and/or ofN-methylglycine (sarcosides). Particular preference here is given to thesarcosides and/or the sarcosinates and here in particular sarcosinatesof higher and optionally mono- or polyunsaturated fatty acids such asoleyl sarcosinate.

Further suitable anionic surfactants are sulphated fatty acid glycerolesters. Fatty acid glycerol esters are to be understood as meaning themono-, di- and triesters, as well as mixtures thereof, as are obtainedduring the production by esterification of a monoglycerol with 1 to 3mol of fatty acid or during the transesterification of triglycerideswith 0.3 to 2 mol of glycerol. Preferred sulphated fatty acid glycerolesters here are the sulphation products of saturated fatty acids having6 to 22 carbon atoms, for example caproic acid, caprylic acid, capricacid, myristic acid, lauric acid, palmitic acid, stearic acid or behenicacid.

Preferred alk(en)yl sulphates are the alkali metal and in particular thesodium salts of the sulphuric acid half-esters of C12-C18-fattyalcohols, for example of coconut fatty alcohol, tallow fatty alcohol,lauryl, myristyl, cetyl or stearyl alcohol or of the C10-C20-oxoalcohols and those half-esters of secondary alcohols of these chainlengths. Furthermore, preference is given to alk(en)yl sulphates of thestated chain length which contain a synthetic, petrochemical-basedstraight-chain alkyl radical and which have an analogous degradationbehaviour to the equivalent compounds based on fatty chemical rawmaterials. From a washing point of view, the C12-C16-alkyl sulphates andC12-C15-alkyl sulphates, and C14-C15-alkyl sulphates are preferred.2,3-Alkyl sulphates, which can be obtained for example as commercialproducts of the Shell Oil Company under the name DAN(R) are alsosuitable anionic surfactants.

The sulphuric acid monoesters of the straight-chain or branchedC7-21-alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as2-methyl-branched C9-11-alcohols having on average 3.5 mol of ethyleneoxide (EO) or C12-18-fatty alcohols having 1 to 4 EO are also suitable.They are used in cleaners only in relatively small amounts, for examplein amounts of from 1 to 5% by weight, on account of their high foamingbehaviour.

Further suitable anionic surfactants are also the salts ofalkylsulphosuccinic acid, which are also referred to as sulphosuccinatesor as sulphosuccinic acid esters and are the monoesters and/or diestersof sulphosuccinic acid with alcohols, preferably fatty alcohols and inparticular ethoxylated fatty alcohols. Preferred sulphosuccinatescomprise C8-18-fatty alcohol radicals or mixtures of these. Particularlypreferred sulphosuccinates contain a fatty alcohol radical which isderived from ethoxylated fatty alcohols which, when viewed per se, arenonionic surfactants (for description see below). Here, particularpreference is in turn given to sulphosuccinates whose fatty alcoholradicals are derived from ethoxylated fatty alcohols with a narrowedhomologue distribution. It is likewise also possible to usealk(en)ylsuccinic acid having preferably 8 to 18 carbon atoms in thealk(en)yl chain or salts thereof.

Particularly preferred anionic surfactants are soaps. Of suitability aresaturated and unsaturated fatty acid soaps, such as the salts of lauricacid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucicacid and behenic acid, and also in particular soap mixtures derived fromnatural fatty acids, for example coconut, palm kernel, olive oil ortallow fatty acids.

The anionic surfactants including the soaps can be present in the formof their sodium, potassium or ammonium salts, and also in the form ofsoluble salts of organic bases, such as mono-, di- or triethanolamine.Preferably, the anionic surfactants are present in the form of theirsodium or potassium salts, in particular in the form of the sodiumsalts.

The content of anionic surfactants in preferred liquid detergents andcleaners is 1 to 30% by weight, preferably 4 to 25% by weight and inparticular 5 to 22% by weight, in each case based on the totalcomposition. It is particularly preferred that the amount of fatty acidsoap is at least 2% by weight and particularly preferred at least 3% byweight and especially preferred at least 4% by weight.

Suitable further surfactants for producing the detergents or cleanersaccording to the invention are so-called gemini surfactants. These aregenerally understood as meaning those compounds which have twohydrophilic groups and two hydrophobic groups per molecule. These groupsare generally separated from one another by a so-called “spacer”. Thisspacer is generally a carbon chain which should be long enough for thehydrophilic groups to have a sufficient distance so that they can actindependently of one another. Surfactants of this type are characterizedin general by an unusually low critical micelle concentration and theability to greatly reduce the surface tension of the water. Inexceptional cases, however, the expression Gemini surfactants isunderstood as meaning not only dimeric, but also trimeric surfactants.

Gemini surfactants for producing detergents or cleaners are, forexample, sulphated hydroxy mixed ethers according to the German patentapplication DE-A-43 21 022 or dimer alcohol bis- and trimer alcoholtris-sulphates and ether sulphates according to the German patentapplication DE-A-195 03 061. Terminally capped dimeric and trimericmixed ethers according to the German patent application DE-A-195 13 391are characterized in particular by their bi- and multifunctionality. Forexample, the specified terminally capped surfactants have good wettingproperties and in so doing are low-foam, meaning that they are suitablein particular for use in machine washing or cleaning processes.

From an applications point of view, mixtures of anionic and nonionicsurfactants are preferred. The total surfactant content of the liquiddetergent and cleaner is preferably below 40% by weight and particularlypreferably below 35% by weight, based on the total liquid detergent andcleaner.

Builders

Builders which can be present in the liquid detergents and cleaners are,in particular, silicates, aluminium silicates (in particular zeolites),carbonates, organic cobuilders, phosphates, salts of organic di- andpolycarboxylic acids, and mixtures of these substances.

Suitable crystalline, layered sodium silicates have the general formulaNaMSi_(x)O_(2x+1)*H2O,where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is anumber from 0 to 20 and preferred values for x are 2, 3 or 4. Preferredcrystalline sheet silicates of the stated formula are those in which Mis sodium and x assumes the values 2 or 3. In particular, preference isgiven to both beta- and also delta-sodium disilicates Na₂Si₂O₅*yH₂O.

It is also possible to use amorphous sodium silicates with an Na₂O:SiO₂modulus of 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particularfrom 1:2 to 1:2.6, which have delayed dissolution and secondarydetergency properties. The dissolution delay compared with conventionalamorphous sodium silicates can have been brought about here in variousways, for example as result of surface treatment, compounding,compaction/compression or as a result of overdrying. In the context ofthis invention, the term “amorphous” also means “X-ray amorphous”. Thismeans that, in X-ray diffraction experiments, the silicates did notproduce any sharp X-ray reflections, as are typical for crystallinesubstances, but at best have one or more maxima of the scattered X-rayradiation, which have a width of several degree units of the diffractionangle. It can, however, very probably even lead to particularly goodbuilder properties if the silicate particles during electron diffractionexperiments produce indistinct or even jagged diffraction maxima. Thisis to be interpreted in such a way that the products havemicrocrystalline regions of size 10 to a few hundred nm, with values upto at most 50 nm and in particular up to at most 20 nm being preferred.Such so-called X-ray amorphous silicates likewise have a dissolutiondelay compared with conventional waterglasses. Particular preference isgiven to compressed/compacted amorphous silicates, compounded amorphoussilicates and over dried X-ray amorphous silicates.

A finely crystalline, synthetic zeolite containing bonded water that canbe used is preferably zeolite A and/or P. As zeolite P, particularpreference is given to zeolite MAP™ (commercial product of Crosfield).However, also of suitability are zeolite X and mixtures of A, X and/orP. Commercially available and usable with preference in the context ofthe present invention is for example also a cocrystallizate of zeolite Xand zeolite A (about 80% by weight zeolite X), which is sold by SASOLunder the trade name VEGOBOND AX(R) and can be described by the formulanNa2O*(1−n)K₂O*Al₂O₃.(2-2.5)*SiO₂.(3.5-5.5)*H₂O.

The zeolite can be used in the form of a spray-dried powder or else asan undried, stabilized suspension that is still wet from itspreparation. If the zeolite is used as a suspension, this can comprisesmall additives of nonionic surfactants as stabilizers, for example 1 to3% by weight, based on zeolite, of ethoxylated C₁₂-C₁₈-fatty alcoholswith 2 to 5 ethylene oxide groups, C₁₂-C₁₄-fatty alcohols with 4 to 5ethylene oxide groups or ethoxylated isotridecanols. Suitable zeoliteshave an average particle size of less than 10 μm (volume distribution;measurement method: Coulter counter) and comprise preferably 18 to 22%by weight, in particular 20 to 22% by weight, of bonded water.

It is of course also possible to use the generally known phosphates asbuilder substances provided such a use should not be avoided forecological reasons. Of suitability are in particular the sodium salts ofthe orthophosphates, the pyrophosphates and in particular thetripolyphosphates.

Suitable builders are organic cobuilders, in particularpolycarboxylates/polycarboxylic acids, polymeric polycarboxylates,aspartic acid, polyacetals, dextrins, and phosphonates.

Polymeric polycarboxylates are for example the alkali metal salts ofpolyacrylic acid or of polymethacrylic acid, for example those with arelative molecular mass of from 500 to 70 000 g/mol. The molar massesstated for polymeric polycarboxylates in the context of thisspecification are weight-average molar masses Mw of the particular acidform, which have been determined in principle by means of gel permeationchromatography (GPC), using a UV detector. The measurement was carriedout here against an external polyacrylic acid standard, which producesrealistic molecular weight values on account of its structuralsimilarity to the investigated polymers. This data differs significantlyfrom molecular weight data for which polystyrene sulphonic acids areused as the standard. The molar masses measured against polystyrenesulphonic acids are generally considerably higher than the molar massesstated in this specification.

Suitable polymers are in particular polyacrylates, which preferably havea molecular mass of from 2000 to 20 000 g/mol. On account of theirsuperior solubility the short-chain polyacrylates, which have molarmasses of from 2000 to 10 000 g/mol, and particularly preferably from3000 to 5000 g/mol, can in turn be preferred from this group.

Also of suitability are copolymeric polycarboxylates, in particularthose of acrylic acid with methacrylic acid and of acrylic acid ormethacrylic acid with maleic acid. Copolymers of acrylic acid withmaleic acid which comprise 50 to 90% by weight of acrylic acid and 50 to10% by weight of maleic acid have proven to be particularly suitable.Their relative molecular mass, based on free acids, is generally 2000 to70 000 g/mol, preferably 20 000 to 50 000 g/mol and in particular 30 000to 40 000 g/mol.

Of particular preference are also biodegradable polymers of more thantwo different monomer units, for example those which comprise, asmonomers, salts of acrylic acid and of maleic acid, and also vinylalcohol or vinyl alcohol derivatives or which comprise, as monomers,salts of acrylic acid and of 2-alkylallylsulphonic acid, and sugarderivatives.

Further preferred copolymers are those which have, as monomers,preferably acrolein and acrylic acid/acrylic acid salts or acrolein andvinyl acetate.

Polymeric aminodicarboxylic acids, salts thereof or precursor substancesthereof are likewise to be mentioned as further preferred buildersubstances. Of particular preference are polyaspartic acids and saltsand derivatives thereof which, besides cobuilder properties, also have ableach-stabilizing effect.

Further suitable builder substances are polyacetals which can beobtained by reacting dialdehydes with polyolcarboxylic acids which have5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferredpolyacetals are obtained from dialdehydes such as glyoxal,glutaraldehyde, terephthalaldehyde, and mixtures thereof and frompolyolcarboxylic acids such as gluconic acid and/or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for exampleoligomers and polymers of carbohydrates which can be obtained by partialhydrolysis of starches. The hydrolysis can be carried out according tocustomary, for example acid- or enzyme-catalysed, processes. Thehydrolysis products are preferably those with average molar masses inthe range from 400 to 500 000 g/mol. Here, a polysaccharide with adextrose equivalent (DE) in the range from 0.5 to 40, in particular from2 to 30, is preferred, with DE being a customary measure of the reducingeffect of a polysaccharide compared to dextrose, which has a DE of 100.It is possible to use either maltodextrins with a DE between 3 and 20and dry glucose syrups with a DE between 20 and 37 or so-called yellowdextrins and white dextrins with higher molar masses in the range from2000 to 30 000 g/mol.

The oxidized derivatives of such dextrins are the reaction productsthereof with oxidizing agents, which are able to oxidize at least onealcohol function of the saccharide ring to the carboxylic acid function.A product oxidized on C6 of the saccharide ring can be particularlyadvantageous.

A preferred dextrin is described in the British patent application GB9,419,091 B1. The oxidized derivatives of such dextrins are theirreaction products with oxidizing agents which are able to oxidize atleast one alcohol function of the saccharide ring to the carboxylic acidfunction. Oxidized dextrins of this type and processes for theirpreparation are known for example from the European patent applicationsEP 032202 A, EP 0427349 A, EP 0472042 A and EP 0542496 A, and theinternational patent applications WO 1992/018542 A, WO 1993/008251 A, WO1994/028030 A, WO 1995/007303 A, WO 1995/012619 A and WO 1995/020608 A.A product oxidized on C₆ of the saccharide ring can be particularlyadvantageous.

Oxydisuccinates and other derivatives of disuccinates, preferablyethylenediamine disuccinate, are also further suitable cobuilders. Here,ethylenediamine N,N′-disuccinate (EDDS) is preferably used in the formof its sodium or magnesium salts. Furthermore, preference is given inthis connection also to glycerol disuccinates and glyceroltrisuccinates, as are described for example in the US-American patentspecifications U.S. Pat. Nos. 4,524,009, 4,639,325, in the Europeanpatent application EP 0150930 A and the Japanese patent application JP1993/339896 A.

Further organic cobuilders that can be used are, for example, acetylatedhydroxycarboxylic acids and salts thereof, which can optionally also bepresent in lactone form and which contain at least 4 carbon atoms and atleast one hydroxy group, and at most two acid groups. Cobuilders of thiskind are described for example in the International patent applicationWO 1995/020029 A.

A further substance class with cobuilder properties is the phosphonates.These are in particular hydroxyalkane- and aminoalkanephosphonates.Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate(HEDP) is of particular importance as cobuilder. It is preferably usedas sodium salt, with the disodium salt giving a neutral reaction and thetetrasodium salt giving an alkaline (pH 9) reaction. Suitableaminoalkanephosphonates are preferablyethylenediaminetetramethylenephosphonate (EDTMP),diethylenetriaminepentamethylenephosphonate (DTPMP), and higherhomologues thereof. They are preferably used in the form of the neutralreacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- andocta-sodium salt of DTPMP. The builder used here from the class ofphosphonates is preferably HEDP. The aminoalkanephosphonates, moreover,have a marked heavy metal binding capacity. Accordingly, it may bepreferred, especially if the detergents and cleaners also comprisebleach, to use aminoalkanephosphonates, in particular DTPMP, or to usemixtures of the stated phosphonates for producing the composition.

Moreover, all compounds which are able to form complexes with alkalineearth metal ions can be used as co-builders.

Further organic builder substances that can be used are also thepolycarboxylic acids that can be used in the form of their sodium salts,with polycarboxylic acids being understood as meaning those carboxylicacids which carry more than one acid function. For example, these arecitric acid, adipic acid, succinic acid, glutaric acid, malic acid,tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylicacids, nitrilotriacetic acid (NTA), provided such a use is notobjectionable for ecological reasons, and mixtures of these. Preferredsalts are the salts of the polycarboxylic acids such as citric acid,adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acidsand mixtures of these.

The acids per se can also be used. Besides their builder effect, theacids typically also have the property of an acidifying component andthus also serve to establish a lower and more mild pH of detergentsand/or cleaners. In particular, mention is to be made here of citricacid, succinic acid, glutaric acid, adipic acid, gluconic acid and anydesired mixtures of these.

Bleaches and Bleach Catalysts

Among the compounds which produce H2O2 in water and serve as bleaches,sodium perborate tetrahydrate and sodium perborate monohydrate haveparticular importance. Further bleaches that can be used are, forexample, sodium percarbonate, peroxypyrophosphates, citrate perhydrates,and also H2O2-producing peracidic salts or peracids, such asperbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacidor diperdodecanedioic acid. In order to achieve an improved bleachingeffect upon washing at temperatures of 60° C. and below, bleachactivators can be incorporated into the detergents and cleaners. Bleachactivators that can be used are compounds which, under perhydrolysisconditions, produce aliphatic peroxocarboxylic acids having preferably 1to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionallysubstituted perbenzoic acid. Of suitability are substances which carrythe O- and/or N-acyl groups of the stated number of carbon atoms and/oroptionally substituted benzoyl groups. Preference is given topolyacylated alkylene diamines, in particular tetraacetylethylenediamine(TAED), acylated triazine derivatives, in particular1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylatedglycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides,in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulphonates,in particular nonanoyl- or isononanoyloxybenzene sulphonate (n- oriso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride,acylated polyhydric alcohols, in particular triacetin, ethylene glycoldiacetate and 2,5-diacetoxy-2,5-dihydrofuran. In addition to theconventional bleach activators or instead of them, it is also possiblefor so-called bleach catalysts to be incorporated into the textiletreatment compositions. These substances are bleach-enhancing transitionmetal salts or transition metal complexes such as, for example, Mn-,Fe-, Co-, Ru- or Mo-salen complexes or -carbonyl complexes. Mn, Fe, Co,Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands,and Co-, Fe-, Cu- and Ru-ammine complexes can also be used as bleachcatalysts.

Thickeners

A liquid detergent and cleaner can comprise a thickener. The thickenercan comprise, for example, a polyacrylate thickener, xanthan gum, gellangum, guar seed flour, alginate, carrageenan, carboxymethylcellulose,bentonite, wellan gum, carob seed flour, agar agar, tragacanth, gumarabic, pectins, polyoses, starch, dextrins, gelatine and casein.However, modified natural substances such as modified starches andcelluloses can also be used as thickeners, examples here beingcarboxymethylcellulose and other cellulose ethers, hydroxyethyl- and-propylcellulose, and seed flour ethers.

The polyacrylic and polymethacrylic thickeners include, for example, thehigh molecular weight homopolymers of acrylic acid crosslinked with apolyalkenyl polyether, in particular an allyl ether of sucrose,pentaerythritol or propylene (INCI name according to “InternationalDictionary of Cosmetic Ingredients” of The Cosmetic, Toiletry andFragrance Association (CTFA): Carbomer), which are also referred to ascarboxyvinyl polymers. Such polyacrylic acids are available inter aliafrom 3V Sigma under the trade name Polygel®, e.g. Polygel DA, and fromB.F. Goodrich under the trade name Carbopol®, e.g. Carbopol 940(molecular weight about 4 000 000), Carbopol 941 (molecular weight about1 250 000) or Carbopol 934 (molecular weight about 3 000 000).Furthermore, these include the following acrylic acid copolymers: (i)copolymers of two or more monomers from the group of acrylic acid,methacrylic acid and its simple esters formed preferably withC1-4-alkanols (INCI Acrylates Copolymer), which include for example thecopolymers of methacrylic acid, butyl acrylate and methyl methacrylate(CAS name according to Chemical Abstracts Service: 25035-69-2) or ofbutyl acrylate and methyl methacrylate (CAS 25852-37-3) and which areavailable for example by Rohm and Haas under the trade names Aculyn® andAcusol®, and also by Degussa (Goldschmidt) under the trade name Tego®Polymer, e.g. the anionic nonassociative polymers Aculyn 22, Aculyn 28,Aculyn 33 (crosslinked), Acusol 810, Acusol 820, Acusol 823 and Acusol830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylicacid copolymers, which include for example the copolymers, crosslinkedwith an allyl ether of sucrose or of pentaerythritol, of C10-30-alkylacrylates with one or more monomers from the group of acrylic acid,methacrylic acid and their simple esters, formed preferably withC1-4-alkanols (INCI Acrylates/C10-30 Alkyl Acrylate Crosspolymer) andwhich are available for example from B.F. Goodrich under the trade nameCarbopol®, e.g. the hydrophobicized Carbopol ETD 2623 and Carbopol 1382(INCI Acrylates/C10-30 Alkyl Acrylate Crosspolymer), and Carbopol Aqua30 (formerly Carbopol EX 473).

A further polymeric thickener to be used with preference is xanthan gum,a microbial anionic heteropolysaccharide which is produced fromxanthomonas campestris and a few other species under aerobic conditionsand has a molar mass of from 2 to 15 million Daltons. Xanthan is formedfrom a chain with beta-1,4-bonded glucose (cellulose) with side chains.The structure of the subgroups consists of glucose, mannose, glucuronicacid, acetate and pyruvate, where the number of pyruvate unitsdetermines the viscosity of the xanthan gum. Suitable thickeners are inparticular also a fatty alcohol. Fatty alcohols can be branched orunbranched and of native origin or petrochemical origin. Preferred fattyalcohols have a carbon chain length of from 10 to 20 carbon atoms,preferably 12 to 18. Preference is given to using mixtures of differentcarbon chain lengths, such as tallow fatty alcohol or coconut fattyalcohol. Examples are Lorol® Spezial (C12-14-ROH) or Lorol® Technisch(C12-18-ROH) (both from Cognis). Preferred liquid detergents andcleaners comprise, based on the total composition, 0.01 to 3% by weightand preferably 0.1 to 1% by weight, of thickeners. The amount ofthickener used here is dependent on the type of thickener and thedesired degree of thickening.

Enzymes

The detergents and cleaners can comprise enzymes in encapsulated formand/or directly in the detergents and cleaners. Suitable enzymes are inparticular those from the classes of the hydrolases, such as theproteases, esterases, lipases or lipolytically active enzymes, amylases,cellulases or other glycosyl hydrolases, hemicellulase, cutinases,betaglucanases, oxidases, peroxidases, perhydrolases and/or laccases andmixtures of said enzymes. All of these hydrolases contribute in thewashing to the removal of stains such as protein-, grease- orstarch-containing stains and grey discolorations. Cellulases and otherglycosyl hydrolases can, moreover, contribute as result of the removalof pilling and microfibrills to colour retention and to increasing thesoftness of the textile. Oxidoreductases can also be used for bleachingand/or for inhibiting colour transfer. Of particularly good suitabilityare enzymatic active ingredients obtained from bacteria strains or fungisuch as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseusand Humicola insolens. Preference is given to using proteases of thesubtilisin type and in particular proteases which are obtained fromBacillus lentus. Here, enzyme mixtures, for example of protease andamylase or protease and lipase or lipolytically active enzymes orprotease and cellulase or from cellulase and lipase or lipolyticallyactive enzymes or from protease, amylase and lipase or lipolyticallyactive enzymes or protease, lipase or lipolytically active enzymes andcellulase, but in particular protease and/or lipase-containing mixturesor mixtures with lipolytically active enzymes are of particularinterest. Examples of such lipolytically active enzymes are the knowncutinases. Peroxidases or oxidases have also in some cases proven to besuitable. Suitable amylases include in particular alpha-amylases,isoamylases, pullulanases and pectinases. The cellulases used arepreferably cellobiohydrolases, endoglucanases and p-glucosidases, whichare also called cellobiases, or mixtures of these. Since differentcellulase types differ by virtue of their CMCase and avicelaseactivities, the desired activities can be established through targetedmixtures of the cellulases.

The enzymes can be adsorbed to carrier substances in order to protectthem from premature decomposition. The fraction of the enzymes, of theenzyme liquid formulation(s) or of the enzyme granules directly indetergents and cleaners can be for example about 0.01 to 5% by weight,preferably 0.12 to about 2.5% by weight.

However, it may also be preferred, for example in the case of specialdetergents and cleaners for consumers with allergies, that the detergentand cleaner comprises no enzymes.

Electrolytes

A broad number of highly diverse salts can be used as electrolytes fromthe group of the inorganic salts. Preferred cations are the alkali metaland alkaline earth metals, preferred anions are the halides andsulphates. From a production point of view, the use of NaCl or MgCl₂ inthe detergents and cleaners is preferred. The fraction of electrolytesin the detergents and cleaners is usually 0.1 to 5% by weight.

Solvents

Nonaqueous solvents which can be used in the liquid detergents andcleaners originate for example from the group of the mono- or polyhydricalcohols, alkanolamines or glycol ethers, provided they are misciblewith water in the stated concentration range. The solvents arepreferably selected from ethanol, n- or isopropanol, butanols, glycol,propane- or butanediol, glycerol, diglycol, propyl or butyl diglycol,hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethylether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether,diethylene glycol methyl ether, diethylene glycol ethyl ether, propyleneglycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or-ethyl ether, diisopropylene glycol monomethyl or -ethyl ether,methoxy-, ethoxy- or butoxytriglycol, 1-butoxyethoxy-2-propanol,3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, and mixturesof these solvents. Nonaqueous solvents can be used in the liquiddetergents and cleaners in amounts between 0.5 and 15% by weight, butpreferably below 12% by weight and in particular below 9% by weight.

Viscosity

The viscosity of the detergents and cleaners in liquid form can bemeasured using customary standard methods (for example Brookfieldviscometer LVT-II at 20 rpm and 20° C., spindle 3) and is for liquiddetergents preferably in the range from 500 to 5000 mPas. Preferably,liquid detergents and cleaners have viscosities of from 700 to 4000mPas, with values between 1000 and 3000 mPas being particularlypreferred. The viscosity of fabric softeners is preferably 20 to 4000mPas, with values between 40 and 2000 mPas being particularly preferred.The viscosity of fabric softeners is particularly preferably from 40 to1000 mPas.

pH Regulators

In order to bring the pH of the liquid detergents and cleaners into thedesired range, the use of pH regulators may be appropriate. Here, it ispossible to use all known acids or alkalis provided their use is notruled out for application-related or ecological reasons or for reasonsof consumer protection. Usually, the amount of these extenders does notexceed 7% by weight of the total formulation. The pH of liquiddetergents and cleaners is preferably between 4 and 10 and preferablybetween 5.5 and 8.5. The pH of liquid fabric softeners is preferablybetween 1 and 6 and preferably between 1.5 and 3.5.

Dyes

In order to improve the aesthetic impression of the textile treatmentcompositions, they can be coloured with suitable dyes. Preferred dyes,the selection of which does not present the person skilled in the artwith any difficulty, have a high storage stability and insensitivity tothe other ingredients of the detergents and cleaners and to light and nomarked substantivity towards textile fibres, so as not to stain these.

Antiredeposition Agents

Suitable soil release polymers, which are also referred to as“antiredeposition agents”, are for example nonionic cellulose etherssuch as methyl cellulose and methylhydroxypropyl cellulose with afraction of methoxy groups of from 15 to 30% by weight and ofhydroxypropyl groups of from 1 to 15% by weight, in each case based onthe nonionic cellulose ethers, as well as the polymers, known from theprior art, of phthalic acid and/or terephthalic acid or of derivativesthereof, in particular polymers of ethylene terephthalates and/orpolyethylene and/or polypropylene glycol terephthalates or anionicallyand/or nonionically modified derivatives of these. Suitable derivativesinclude the sulphonated derivatives of phthalic acid and terephthalicacid polymers.

Optical Brighteners

Optical brighteners (so-called “white toners”) can be added to thedetergents and cleaners in order to eliminate greying and yellowing ofthe treated fabrics. These substances attach to the fibres and bringabout a lightening and pretend bleaching effect by converting invisibleultraviolet radiation into visible long-wave light, the ultravioletlight absorbed from the sunlight being irradiated as slightly bluishfluorescence and producing pure white with the yellow shade of thegreyed or yellowed laundry. Suitable compounds originate for examplefrom the substance classes of the 4,4′-diamino-2,2′-stilbenedisulphonicacids (flavone acids), 4,4′-distyrylbiphenyls, methylumbelliferones,coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides,benzoxazole, benzisoxazole and benzimidazole systems, as well as thepyrene derivatives substituted by heterocycles. The optical brightenersare usually used in amounts between 0% and 0.3% by weight, based on thefinished detergent and cleaner.

Greying Inhibitors

Greying inhibitors have the task of keeping the dirt detached from thefibres suspended in the liquor and in so doing of preventingreattachment of the dirt. For this purpose, water-soluble colloids of amostly organic nature are suitable, for example size, gelatine, salts ofether sulphonic acids or starch or of cellulose or salts of acidicsulphuric acid esters of cellulose or of starch. Water-solublepolyamides containing acidic groups are also suitable for this purpose.Furthermore, it is possible to use soluble starch preparations andstarch products other than those specified above, for example degradedstarch, aldehyde starches etc. Polyvinylpyrrolidone can also be used.However, preference is given to using cellulose ethers such ascarboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcelluloseand mixed ethers such as methylhydroxyethylcellulose,methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixturesthereof in amounts of from 0.1 to 5% by weight, based on the detergentsand cleaners.

Anticrease Agents

Since fabrics, in particular made of rayon, spun rayon, cotton andmixtures thereof, can have a tendency to crease because the individualfibres are sensitive to bending, crinkling, pressing and squashingtransverse to the fibre direction, the detergents and cleaners cancomprise synthetic anticrease agents. These include, for example,synthetic products based on fatty acids, fatty acid esters, fatty acidamides, fatty acid alkylol esters, fatty acid alkylolamides or fattyalcohols, which are mostly reacted with ethylene oxide, or productsbased on lecithin or modified phosphoric acid esters.

Antimicrobial Active Ingredients

To control microorganisms, the detergents and cleaners can compriseantimicrobial active ingredients. A distinction is made here, accordingto the antimicrobial spectrum and mechanism of action, betweenbacteriostats and bacteriocides, fungistats and fungicides etc.Important substances from these groups are, for example,benzalkoniumchlorides, alkylarylsulphonates, halophenols andphenolmercuriacetate, it also being possible to dispense entirely withthese compounds in the case of the detergents and cleaners according tothe invention.

Preservatives

The detergents and cleaners according to the invention can comprisepreservatives, in which case preferably only those are used which have,if any, only a slight skin-sensitizing potential. Examples are sorbicacid and its salts, benzoic acid and its salts, salicylic acid and itssalts, phenoxyethanol, 3-iodo-2-propynyl butylcarbamate, sodiumN-(hydroxymethyl)glycinate, biphenyl-2-ol, and mixtures thereof. Asuitable preservative is the solvent-free, aqueous combination ofdiazolidinylurea, sodium benzoate and potassium sorbate (available asEuxyl® K 500ex Schülke and Mayr), which can be used in a pH range up to7. Of particular suitability are preservatives based on organic acidsand/or salts thereof for preserving the skin-friendly detergents andcleaners according to the invention.

Antioxidants

In order to prevent undesired changes to the detergents and cleanersand/or the treated fabrics caused by the action of oxygen and otheroxidative processes, the detergents and cleaners can compriseantioxidants. This compound class includes, for example, substitutedphenols, hydroquinones, pyrocatechins and aromatic amines, and alsoorganic sulphides, polysulphides, dithiocarbamates, phosphites,phosphonates and vitamin E.

Antistatic Agents

Increased wear comfort can result from the additional use of antistaticagents which are additionally added to the detergents and cleaners.Antistatic agents increase the surface conductivity and thus allow animproved discharging of charges formed. Antistatic agents are generallysubstances with at least one hydrophilic molecular ligand and give amore or less hygroscopic film on the surfaces. These mostlyinterface-active antistatic agents can be divided intonitrogen-containing ones (amines, amides, quaternary ammoniumcompounds), phosphorus-containing ones (phosphoric acid esters) andsulphur-containing ones (alkylsulphonates, alkylsulphates). Lauryl-(orstearyl-)dimethylbenzylammonium chlorides are suitable as antistaticagents for fabrics and/or as additive for detergents and cleaners, inwhich case a finishing effect is additionally achieved.

Foam Inhibitors

To improve the rewettability of the treated fabrics and to facilitateironing of the treated fabrics, silicone derivatives, for example, canbe used in the textile treatment compositions. These additionallyimprove the rinse-out behaviour of the detergents and cleaners by virtueof their foam-inhibiting properties. Preferred silicone derivatives are,for example, polydialkyl- or alkylarylsiloxanes in which the alkylgroups have one to five carbon atoms and are completely or partiallyfluorinated. Preferred silicones are polydimethylsiloxanes, which canoptionally be derivatized and are then amino functional or quaternizedand/or have Si—OH, Si—H and/or Si—Cl bonds. The viscosities of thepreferred silicones at 25° C. are in the range between 100 and 100 000mPas, where the silicones can be used in amounts between 0.2 and 5% byweight, based on the total detergent and cleaner.

UV Absorbers

Finally, the detergents and cleaners can also comprise UV absorbers,which attach to the treated fabrics and improve the light resistance ofthe fibres. Compounds which have these desired properties are, forexample, the compounds effective as a result of radiationlessdeactivation and derivatives of benzophenone with substituents in the 2and/or 4 position. Furthermore of suitability are also substitutedbenzotriazoles, 3-phenyl-substituted acrylates (cinnamic acidderivatives), optionally with cyano groups in the 2 position,salicylates, organic Ni complexes, and natural substances such asumbelliferone and endogeneous urocanic acid.

Heavy Metal Complexing Agents

In order to avoid the decomposition of certain detergent ingredientscatalysed by heavy metals, it is possible to use substances whichcomplex heavy metals. Suitable heavy metal complexing agents are, forexample, the alkali metal salts of ethylenediaminetetraacetic acid(EDTA) or of nitrilotriacetic acid (NTA), and also alkali metal salts ofanionic polyelectrolytes such as polymaleates and polysulphonates. Apreferred class of complexing agents is the phosphonates, which arepresent in preferred textile treatment compositions in amounts of from0.01 to 2.5% by weight, preferably 0.02 to 2% by weight and inparticular from 0.03 to 1.5% by weight. These preferred compoundsinclude in particular organo-phosphonates such as, for example,1-hydroxyethane-1,1-diphosphonic acid (HEDP),aminotri(methylenephosphonic acid) (ATMP),diethylenetriaminepenta(methylenephosphonic acid) (DTPMP or DETPMP), and2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM), which are mostlyused in the form of their ammonium or alkali metal salts.

Producing the Preparations

The liquid laundry detergents, dishwashing detergents and cleaners areproduced using customary and known methods and processes in which, forexample, the constituents are simply mixed in stirred tanks, with water,nonaqueous solvents and surfactants expediently being added as initialcharge and the other constituents being added in portions. Thus, liquiddetergents and cleaners can be produced by initially introducing theacidic components such as, for example, the linear alkylsulphonates,citric acid, boric acid, phosphonic acid, the fatty alcohol ethersulphates, etc. and the nonionic surfactants. The solvent component ispreferably also added at this point, although the addition can also takeplace at a later time. The polyacrylate is added to these components.Then, a base such as, for example, NaOH, KOH, triethanolamine ormonoethanolamine is added, followed by the fatty acid, if present.Subsequently, the remaining ingredients and the remaining solvents ofthe aqueous liquid detergents and cleaners are added to the mixture andthe pH is adjusted to approximately 8.5. Finally, the particles to bedispersed can be added and distributed homogeneously in the aqueousliquid detergent and cleaner by mixing.

The compositions according to the invention are preferably laundrydetergents which are suitable both for manual for machine washing, inparticular of textiles. They may also be detergents or cleaners for theindustrial sector or for the household sector. Cleaners can be used forexample also for cleaning hard surfaces. These may for example bedishwashing detergents which are used for the manual or machine cleaningof dishes. They may also be customary industrial or household cleanerswith which hard surfaces such as furniture surfaces, tiles, wall andfloor coverings are cleaned. Besides dishes, hard surfaces also includeall customary hard surfaces, in particular made of glass, ceramic,plastic or metal, domestically and in industry.

Here, the detergents and cleaners are preferably liquid formulationswhich may be solutions, emulsions, dispersions, suspensions,microemulsions, gels or pastes.

As surface treatment agents, the composition can accordingly comprisecustomary ingredients of cleaners in customary amounts. For example,surface treatment compositions in the form of cleaners can comprisealkyl ether sulphates, alkyl- and/or arylsulphonates, alkyl sulphates,amphoteric surfactants, anionic surfactants, nonionic surfactants,cationic surfactants, solvents, thickeners, dicarboxylic acid (salts)and further auxiliaries and additives.

These additional ingredients have in part already been explained in moredetail above and are likewise valid here for use in cleaners (see e.g.nonionic surfactants). Auxiliaries and additives which may bepresent—especially in hand dishwashing detergents and cleaners for hardsurfaces—are in particular UV stabilizers, perfume, pearlizing agents(INCI Opacifying Agents; for example glycol distearate, e.g. Cutina® AGSfrom Henkel KGaA, or mixtures containing this, e.g. the Euperlans® fromHenkel KGaA), SRP (soil repellent polymers), PEG terephthalates, dyes,bleaches (e.g. hydrogen peroxide), corrosion inhibitors, preservatives(e.g. the 2-bromo-2-nitropropane-1,3-diol technically also referred toas bronopol (CAS 52-51-7), which is commercially available for exampleas Myacide® BT or as BootsBronopol BT from Boots), andskin-feel-improving or care additives (e.g. dermatologically effectivesubstances such as vitamin A, vitamin B2, vitamin B12, vitamin C,vitamin E, D-panthenol, sericerin, collagen partial hydrolysate, variousplant protein partial hydrolysates, protein hydrolysate fatty acidcondensates, liposomes, polypropylene glycol, Nutrilan™ Chitosan™,cholesterol, vegetable and animal oils such as e.g. lecithin, soybeanoil, etc., plant extracts such as e.g. aloe vera, azulene, hamamelisextracts, algae extracts, etc., allantoin, A.H.A. complexes, in amountsof usually not more than 5% by weight. To enhance performance, smallamounts of enzymes can be used. Preference is given to proteases (e.g.BLAP (Henkel), savinase (NOVO), durazym (NOVO), maxapemm, etc.),amylases (e.g. fermamyl (NOVO), etc.), lipases (e.g. lipolase (NOVO),etc.), peroxidases, gluconases, cellulases, mannases, etc., in amountsof preferably 0.001 to 1.5% by weight and particularly preferably lessthan 0.5% by weight.

Cosmetic Preparations

A further subject matter of the invention relates to cosmeticpreparations at least four lactones selected from the group consistingof γ-hexalactone, γ-heptalactone, γ-octalactone, γ-nonalactone,γ-decalactone, γ-undecalactone, γ-dodecalactone, δ-hexalactone,δ-heptalactone, δ-octalactone, δ-nonalactone, δ-decalactone,δ-undecalactone, δ-dodecalactone, and mixtures thereof, where the useconcentration of the lactone or of the lactones is usually in the rangefrom 0.01 to 1% by weight, preferably 0.1 to 0.5% by weight—based on thepreparations.

The cosmetic compositions according to the invention can comprisefurther typical auxiliaries and additives, such as, for example, mildsurfactants, oil bodies, emulsifiers, pearlescent waxes, consistencyregulators, thickeners, superfatting agents, stabilizers, polymers,silicone compounds, fats, waxes, lecithins, phospholipids, UV lightprotection factors, humectants, biogenic active ingredients,antioxidants, deodorants, antiperspirants, antidandruff agents, filmformers, swelling agents, insect repellants, self-tanning agents,tyrosine inhibitors (depigmentation agents), hydrotropes, solubilizers,preservatives, perfume oils, dyes and the like.

Surfactants

Surface-active substances that can be present are anionic, nonionic,cationic and/or amphoteric or zwitterionic surfactants, the fraction ofwhich in the compositions is usually about 1 to 70, preferably 5 to 50and in particular 10 to 30% by weight. Typical examples of anionicsurfactants are soaps, alkylbenzenesulphonates, alkanesulphonates,olefinsulphonates, alkyl ether sulphonates, glycerol ether sulphonates,α-methyl ester sulphonates, sulpho fatty acids, alkyl sulphates, alkylether sulphates, glycerol ether sulphates, fatty acid ether sulphates,hydroxy mixed ether sulphates, monoglyceride (ether) sulphates, fattyacid amide (ether) sulphates, mono- and dialkyl sulphosuccinates, mono-and dialkyl sulphosuccinamates, sulphotriglycerides, amide soaps, ethercarboxylic acids and salts thereof, fatty acid isethionates, fatty acidsarcosinates, fatty acid taurides, N-acylamino acids, such as, forexample, acyl lactylates, acyl tartrates, acyl glutamates and acylaspartates, alkyl oligoglucoside sulphates, protein fatty acidcondensates (in particular plant products based on wheat) andalkyl(ether)phosphates. If the anionic surfactants contain polyglycolether chains, these can have a conventional homologue distribution, butpreferably have a narrowed homologue distribution. Typical examples ofnonionc surfactants are fatty alcohol polyglycol ethers, alkylphenolpolyglycol ethers, fatty acid polyglycol esters, fatty acid amidepolyglycol ethers, fatty amine polyglycol ethers, alkoxylatedtriglycerides, mixed ethers and mixed formals, optionally partiallyoxidized alk(en)yl oligoglycosides and glucuronic acid derivatives,fatty acid N-alkylglucamides, protein hydrolysates (in particular plantproducts based on wheat), polyol fatty acid esters, sugar esters,sorbitan esters, polysorbates and amine oxides. If the nonionicsurfactants contain polyglycol ether chains, these can have aconventional homologue distribution, but preferably have a narrowedhomologue distribution. Typical examples of cationic surfactants arequaternary ammonium compounds, such as, for example,dimethyldistearylammonium chloride, and ester quats, in particularquaternized fatty acid trialkanolamine ester salts. Typical examples ofamphoteric or zwitterionic surfactants are alkylbetaines,alkylamidobetaines, aminopropionates, aminoglycinates,imidazoliniumbetaines and sulphobetaines. Said surfactants areexclusively known compounds. Typical examples of particularly suitablemild, i.e. particularly skin-compatible surfactants are fatty alcoholpolyglycol ether sulphates, monoglyceride sulphates, mono- and/ordialkyl sulphosuccinates, fatty acid isethionates, fatty acidsarcosinates, fatty acid taurides, fatty acid glutamates, α-olefinsulphonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acidglucamides, alkylamidobetaines, amphoacetals and/or protein fatty acidcondensates, the latter preferably based on wheat proteins.

Oil Bodies

Suitable oil bodies are, for example, Guerbet alcohols based on fattyalcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters oflinear C₆-C₂₂-fatty acids with linear or branched C₆-C₂₂-fatty alcoholsor esters of branched C₆-C₁₃-carboxylic acids with linear or branchedC₆-C₂₂-fatty alcohols, such as e.g. myristyl myristate, myristylpalmitate, myristyl stearate, myristyl isostearate, myristyl oleate,myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate,cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetylerucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearylisostearate, stearyl oleate, stearyl behenate, stearyl erucate,isostearyl myristate, isostearyl palmitate, isostearyl stearate,isostearyl isostearate, isostearyl oleate, isostearyl behenate,isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate,oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenylmyristate, behenyl palmitate, behenyl stearate, behenyl isostearate,behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate,erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate,erucyl behenate and erucyl erucate. Also of suitability are esters oflinear C₆-C₂₂-fatty acids with branched alcohols, in particular2-ethylhexanol, esters of C₁₈-C₃₈-alkylhydroxycarboxylic acids withlinear or branched C₆-C₂₂-fatty alcohols, in particular dioctyl malate,esters of linear and/or branched fatty acids with polyhydric alcohols(such as e.g. propylene glycol, dimer diol or trimer triol) and/orGuerbet alcohols, triglycerides based on C₆-C₁₀-fatty acids, liquidmono-/di-/triglyceride mixtures based on C₆-C₁₈-fatty acids, esters ofC₆-C₂₂-fatty alcohols and/or Guerbet alcohols with aromatic carboxylicacids, in particular benzoic acid, esters of C₂-C₁₂-dicarboxylic acidswith linear or branched alcohols having 1 to 22 carbon atoms or polyolshaving 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils,branched primary alcohols, substituted cyclohexanes, linear and branchedC₆-C₂₂-fatty alcohol carbonates, such as e.g. dicaprylyl carbonate(Cetiol® CC), Guerbet carbonates based on fatty alcohols having 6 to 18,preferably 8 to 10, carbon atoms, esters of benzoic acid with linearand/or branched C₆-C₂₂-alcohols (e.g. Finsolv® TN), linear or branched,symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atomsper alkyl group, such as e.g. dicaprylyl ether (Cetiol® OE),ring-opening products of epoxidized fatty acid esters with polyols,silicone oils (cyclomethicones, silicon methicone types etc.) and/oraliphatic or naphthenic hydrocarbons, such as e.g. squalane, squalene ordialkylcyclohexanes.

Emulsifiers

Suitable emulsifiers are, for example, nonionogenic surfactants from atleast one of the following groups:

-   -   addition products of from 2 to 30 mol of ethylene oxide and/or 0        to 5 mol of propylene oxide onto linear fatty alcohols having 8        to 22 carbon atoms, onto fatty acids having 12 to 22 carbon        atoms, onto alkyl phenols having 8 to 15 carbon atoms in the        alkyl group, and alkylamines having 8 to 22 carbon atoms in the        alkyl radical;    -   alkyl and/or alkenyl oligoglycosides having 8 to 22 carbon atoms        in the alk(en)yl radical and ethoxylated analogues thereof;    -   addition products of from 1 to 15 mol of ethylene oxide onto        castor oil and/or hydrogenated castor oil;    -   addition products of from 15 to 60 mol of ethylene oxide onto        castor oil and/or hydrogenated castor oil;    -   partial esters of glycerol and/or sorbitan with unsaturated,        linear or saturated, branched fatty acids having 12 to 22 carbon        atoms and/or hydroxycarboxylic acids having 3 to 18 carbon        atoms, and adducts thereof having 1 to 30 mol of ethylene oxide;    -   partial esters of polyglycerol (average degree of        self-condensation 2 to 8), polyethylene glycol (molecular weight        400 to 5000), trimethylolpropane, pentaerythritol, sugar        alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl        glucoside, butyl glucoside, lauryl glucoside), and        polyglucosides (e.g. cellulose) with saturated and/or        unsaturated, linear or branched fatty acids having 12 to 22        carbon atoms and/or hydroxycarboxylic acids having 3 to 18        carbon atoms, and adducts thereof having 1 to 30 mol of ethylene        oxide;    -   mixed esters of pentaerythritol, fatty acids, citric acid and        fatty alcohol and/or mixed esters of fatty acids having 6 to 22        carbon atoms, methylglucose and polyols, preferably glycerol or        polyglycerol.    -   mono-, di- and trialkyl phosphates, and mono-, di- and/or        tri-PEG alkyl phosphates and salt thereof;    -   wool wax alcohols;    -   polysiloxane-polyalkyl-polyether copolymers and corresponding        derivatives;    -   block copolymers e.g. polyethylene glycol-30        dipolyhydroxystearates;    -   polymer emulsifiers, e.g. Pemulen grades (TR-1, TR-2) from        Goodrich or Cosmedia® SP from Cognis;    -   polyalkylene glycols, and    -   glycerol carbonate.

Particularly suitable emulsifiers are explained in more detail below:

Alkoxylates.

The addition products of ethylene oxide and/or of propylene oxide ontofatty alcohols, fatty acids, alkyl phenols or onto castor oil are known,commercially available products. These are homologue mixtures, theaverage degree of alkoxylation of which corresponds to the ratio of thequantitative amounts of ethylene oxide and/or propylene oxide andsubstrate with which the addition reaction is carried out.C_(12/18)-Fatty acid mono- and diesters of addition products of ethyleneoxide onto glycerol are known as re-fatting agents for cosmeticpreparations.

Alkyl and/or alkenyl oligoglycoside. Alkyl and/or alkenyloligoglycosides, their preparation and their use are known from theprior art. Their preparation takes place in particular by reactingglucose or oligosaccharides with primary alcohols having 8 to 18 carbonatoms. As regards the glycoside radical, both monoglycosides in which acyclic sugar radical is bonded glycosidically to the fatty alcohol, aswell as oligomeric glycosides with a degree of oligomerization topreferably about 8 are suitable. The degree of oligomerization here is astatistical average value which has as its basis a homologuedistribution customary for such technical products.

Partial glycerides. Typical examples of suitable partial glycerides arehydroxystearic acid monoglyceride, hydroxystearic acid diglyceride,isostearic acid monoglyceride, isostearic acid diglyceride, oleic acidmonoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride,ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic aciddiglyceride, linolenic acid monoglyceride, linolenic acid diglyceride,erucic acid monoglyceride, erucic acid diglyceride, tartaric acidmonoglyceride, tartaric acid diglyceride, citric acid monoglyceride,citric acid diglyceride, malic acid monoglyceride, malic aciddiglyceride, and technical-grade mixtures thereof which can also containsmall amounts of triglyceride in secondary amounts from the preparationprocess. Likewise of suitability are addition products of from 1 to 30,preferably 5 to 10, mol of ethylene oxide onto the stated partialglycerides.

Sorbitan esters. Suitable sorbitan esters are sorbitan monoisostearate,sorbitan sesquiisostearate, sorbitan diisostearate, sorbitantriisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitandioleate, sorbitan trioleate, sorbitan monoerucate, sorbitansesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitanmonoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate,sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitansesquihydroxystearate, sorbitan dihydroxystearate, sorbitantrihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate,sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate,sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate,sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate,sorbitan trimaleate, and technical-grade mixtures thereof. Likewise ofsuitability are addition products of from 1 to 30, preferably 5 to 10,mol of ethylene oxide onto the stated sorbitan esters.

Polyglycerol esters. Typical examples of suitable polyglycerol estersare polyglyceryl-2 dipolyhydroxystearate (Dehymuls® PGPH),polyglycerol-3 diisostearate (Lameform® TGI), polyglyceryl-4 isostearate(Isolan® GI 34), polyglyceryl-3 oleate, diisostearoyl polyglyceryl-3diisostearate (Isolan® PDI), polyglyceryl-3 methyl glucose distearate(Tego Care® 450), polyglyceryl-3 beeswax (Cera Bellina®), polyglyceryl-4caprate (Polyglycerol Caprate T2010/90), polyglyceryl-3 cetyl ether(Chimexane® NL), polyglyceryl-3 distearate (Cremophor® GS 32) andpolyglyceryl polyricinoleate (Admul® WOL 1403), polyglyceryl dimerateisostearate, and mixtures thereof. Examples of further suitable polyolesters are the mono-, di- and triesters, optionally reacted with 1 to 30mol of ethylene oxide, of trimethylolpropane or pentaerythritol withlauric acid, coconut fatty acid, tallow fatty acid, palmitic acid,stearic acid, oleic acid, behenic acid and the like.

Anionic emulsifiers. Typical anionic emulsifiers are aliphatic fattyacids having 12 to 22 carbon atoms, such as, for example, palmitic acid,stearic acid or behenic acid, and also dicarboxylic acids having 12 to22 carbon atoms, such as, for example, azelaic acid or sebacic acid.

Amphoteric and cationic emulsifiers. Furthermore, zwitterionicsurfactants can be used as emulsifiers. Zwitterionic surfactants is theterm used to refer to those surface-active compounds which carry atleast one quaternary ammonium group and at least one carboxylate and onesulphonate group in the molecule. Particularly suitable zwitterionicsurfactants are the so-called betaines such as theN-alkyl-N,N-dimethylammonium glycinates, for examplecocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyldimethylammonium glycinate, and2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines having in each case8 to 18 carbon atoms in the alkyl or acyl group, as well ascocoacylaminoethylhydroxyethylcarboxymethyl glycinate. Particularpreference is given to the fatty acid amide derivative known under theCTFA name Cocamidopropyl Betaine. Likewise suitable emulsifiers areampholytic surfactants. Ampholytic surfactants are understood as meaningthose surface-active compounds which, apart from a C_(8/18)-alkyl oracyl group in the molecule, contain at least one free amino group and atleast one —COOH or —SO₃H group and are capable of forming internalsalts. Examples of suitable ampholytic surfactants are N-alkylglycines,N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionicacids and alkylaminoacetic acids having in each case about 8 to 18carbon atoms in the alkyl group. Particularly preferred ampholyticsurfactants are N-cocoalkylaminopropionate,cocoacylaminoethylaminopropionate and C_(12/18)-acylsarcosine. Finally,suitable emulsifiers are also cationic surfactants, with those of theester quat type, preferably methyl-quaternized difatty acidtriethanolamine ester salts, being particularly preferred.

Fats and Waxes

Typical examples of fats are glycerides, i.e. solid or liquid vegetableor animal products which consist essentially of mixed glycerol esters ofhigher fatty acids, and suitable waxes are inter alia natural waxes,such as e.g. candelilla wax, carnauba wax, Japan wax, esparto grass wax,cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax,montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax),uropygial grease, ceresine, ozokerite (earth wax), petrolatum, paraffinwaxes, microwaxes; chemically modified waxes (hard waxes), such as e.g.montan ester waxes, sasol waxes, hydrogenated jojoba waxes, andsynthetic waxes, such as e.g. polyalkylene waxes and polyethylene glycolwaxes. Besides the fats, suitable additional substances are alsofat-like substances, such as lecithins and phospholipids. The termlecithins is understood by the person skilled in the art as meaningthose glycero-phospholipids which are formed from fatty acids, glycerol,phosphoric acid and cholin by esterification. Lecithins are thereforealso often referred to as phosphatidylcholines (PC) in the specialistworld. Examples of natural lecithins that may be mentioned are thekephalins, which are also referred to as phosphatidic acids and arederivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast,phospholipids are usually understood as meaning mono- and preferablydiesters of phosphoric acid with glycerol (glycerol phosphates), whichare generally classed among the fats. In addition, sphingosines andsphingolipids are also suitable.

Pearlescent Waxes

Suitable pearlescent waxes are, for example: alkylene glycol esters,specifically ethylene glycol distearate; fatty acid alkanolamides,specifically coconut fatty acid diethanolamide; partial glycerides,specifically stearic acid monoglyceride; esters of polybasic, optionallyhydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22carbon atoms, specifically long-chain esters of tartaric acid; fattysubstances, such as, for example, fatty alcohols, fatty ketones, fattyaldehydes, fatty ethers and fatty carbonates, which have in total atleast 24 carbon atoms, specifically laurone and distearyl ether; fattyacids such as stearic acid, hydroxystearic acid or behenic acid,ring-opening products of olefin epoxides having 12 to 22 carbon atomswith fatty alcohols having 12 to 22 carbon atoms and/or polyols having 2to 15 carbon atoms and 2 to 10 hydroxyl groups, and mixtures thereof.

Cooling Substances

Cooling substances are compounds which produce a feeling of coldness onthe skin. As a rule, these are menthol compounds which—besides the basicbody menthol itself—are selected for example from the group which isformed by Menthol Methyl Ether, Menthone Glyceryl Acetal (FEMA GRAS¹3807), Menthone Glyceryl Ketal (FEMA GRAS 3808), Menthyl Lactate (FEMAGRAS 3748), Menthol Ethylene Glycol Carbonate (FEMA GRAS 3805), MentholPropylene Glycol Carbonate (FEMA GRAS 3806), Menthyl-N-ethyloxamate,Monomethyl Succinate (FEMA GRAS 3810), Monomenthyl Glutamate (FEMA GRAS4006), Menthoxy-1,2-propanediol (FEMA GRAS 3784),Menthoxy-2-methyl-1,2-propanediol (FEMA GRAS 3849), and also thementhane carboxylic acid esters and amides WS-3, WS-4, WS-5, WS-12,WS-14 and WS-30, and mixtures thereof. ¹ FEMA stands for “Flavor andExtract Manufacturers Association” and GRAS is defined as “GenerallyRegarded As Safe”. A FEMA GRAS designation means that the substance thuslabelled is tested according to standard method and is considered to betoxicologically safe.

A first important representative of these substances is MonomenthylSuccinate (FEMA GRAS 3810). Both the succinate and the analogousMonomenthyl Glutarate (FEMA GRAS 4006) are important representatives ofmonomenthyl esters based on di- and polycarboxylic acids:

Examples of applications of the substances can be found for example inthe documents WO 2003 043431 (Unilever) or EP 1332772 A1 (IFF).

The next important group of menthol compounds preferred in the contextof the invention includes carbonate esters of menthol and polyols, suchas, for example, glycols, glycerol or carbohydrates, such as, forexample, menthol ethylene glycol carbonate (FEMA GRAS 3805=Frescolat®MGC), menthol propylene glycol carbonate (FEMA GRAS 3784=Frescolat®MPC), menthol 2-methyl-1,2-propanediol carbonate (FEMA GRAS 3849) or thecorresponding sugar derivatives. Preference is likewise given to thementhol compounds menthyl lactate (FEMA GRAS 3748=Frescolat® ML) and inparticular menthone glyceryl acetal (FEMA GRAS 3807) or menthoneglyceryl ketal (FEMA GRAS 3808), which is marketed under the nameFrescolat® MGA. Among these substances, menthone glyceryl acetal/ketaland menthyl lactate and also menthol ethylene glycol carbonate andmenthol propylene glycol carbonate, which the applicant sells under thenames Frescolat® MGA, Frescolat® ML, Frescolat® MGC and Frescolat® MPC,have proven to be very particularly advantageous.

In the 1970s, menthol compounds were developed for the first time whichhave a C—C bond in the 3 position and from which likewise a series ofrepresentatives can be used. These substances are generally referred toas WS grades. The basic body is a menthol derivative in which thehydroxyl group is exchanged for a carboxyl group (WS-1). All other WSgrades are derived from this structure, such as for example thepreferred species WS-3, WS-4, WS-5, WS-12, WS-14 and WS-30.

Consistency Regulators and Thickeners

Suitable consistency regulators are primarily fatty alcohols or hydroxyfatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms andin addition partial glycerides, fatty acids or hydroxy fatty acids.Preference is given to a combination of these substances with alkyloligoglucosides and/or fatty acid N-methylglucamides of identical chainlength and/or polyglycerol poly-12-hydroxystearates. Suitable thickenersare for example Aerosil grades (hydrophilic silicas), polysaccharides,in particular xanthan gum, guar guar, agar agar, alginates and tyloses,carboxymethyl cellulose and hydroxyethyl- and hydroxypropylcellulose,also higher molecular weight polyethylene glycol mono- and diesters offatty acids, polyacrylates, (e.g. Carbopols® and Pemulen grades fromGoodrich; Synthalens® from Sigma; Keltrol grades from Kelco; Sepigelgrades from Seppic; Salcare grades from Allied Colloids),polyacrylamides, polymers, polyvinyl alcohol and polyvinylpyrrolidone.Bentonites, such as e.g. Bentone® Gel VS-5PC (Rheox), which is a mixtureof cyclopentasiloxane, disteardimonium hectorite and propylenecarbonate, have also proven to be particularly effective. Also ofsuitability are surfactants, such as, for example, ethoxylated fattyacid glycerides, esters of fatty acids with polyols such as, forexample, pentaerythritol or trimethylolpropane, fatty alcoholethoxylates with a narrowed homologue distribution or alkyloligoglucosides, and also electrolytes such as sodium chloride andammonium chloride.

Superfatting Agents and Stabilizers

Superfatting agents that can be used are substances such as, forexample, lanolin and lecithin, and also polyethoxylated or acylatedlanolin and lecithin derivatives, polyol fatty acid esters,monoglycerides and fatty acid alkanolamides, with the lattersimultaneously serving as foam stabilizers.

Stabilizers that can be used are metal salts of fatty acids, such ase.g. magnesium, aluminium and/or zinc stearates and ricinoleates.

Polymers

Suitable cationic polymers are, for example, cationic cellulosederivatives, such as e.g. a quaternized hydroxyethylcellulose, which isavailable under the name Polymer JR 400® from Amerchol, cationic starch,copolymers of diallylammonium salts and acrylamides, quaternizedvinylpyrrolidone/vinylimidazole polymers, such as e.g. Luviquat® (BASF),condensation products of polyglycols and amines, quaternized collagenpolypeptides, such as, for example, lauryldimonium hydroxypropylhydrolyzed collagen (Lamequat®L/Grunau), quaternized wheat polypeptides,polyethyleneimine, cationic silicone polymers, such as e.g.amodimethicones, copolymers of adipic acid anddimethylaminohydroxypropyl diethylene triamine (Cartaretine®/Sandoz),copolymers of acrylic acid with dimethyldiallylammonium chloride(Merquat® 550/Chemviron), polyaminopolyamides, and crosslinkedwater-soluble polymers thereof, cationic chitin derivatives such as, forexample, quaternized chitosan, optionally in microcrystallinedistribution, condensation products of dihaloalkylene, such as e.g.dibromobutane with bisdialkylamines, such as e.g.bis-dimethylamino-1,3-propane, cationic guar gum, such as e.g. Jaguar®CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium saltpolymers, such as e.g. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 fromMiranol.

Suitable anionic, zwitterionic, amphoteric and nonionic polymers are,for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butylmaleate/isobornyl acrylate copolymers, methyl vinyl ether/maleicanhydride copolymers and esters thereof, uncrosslinked polyacrylic acidsand polyacrylic acids crosslinked with polyols, acrylamidopropyltrimethylammonium chloride/acrylate copolymers, octylacrylamide/methylmethacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropylmethacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinylacetate copolymers, vinylpyrrolidone/dimethylaminoethylmethacrylate/vinylcaprolactam terpolymers, and optionally derivatizedcellulose ethers and silicones.

Silicone Compounds

Suitable silicone compounds are, for example, dimethylpolysiloxanes,methylphenylpolysiloxanes, cyclic silicones, and also amino-,fatty-acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/oralkyl-modified silicone compounds, which can be present at roomtemperature either as a liquid or else in resin form. Also ofsuitability are simethicones, which are mixtures of dimethicones with anaverage chain length of from 200 to 300 dimethylsiloxane units andhydrogenated silicates.

UV Light Protection Factors

UV light protection factors are to be understood as meaning for exampleorganic substances (light protection filters) that are present in liquidor crystalline form at room temperature and which are able to absorbultraviolet rays and release the absorbed energy again in the form oflonger-wave radiation, e.g. heat. Usually, the UV light protectionfactors are present in amounts of from 0.1 to 5 and preferably 0.2 to 1%by weight. UVB filters can be oil-soluble or water-soluble. Examples ofoil-soluble substances are:

-   -   3-benzylidenecamphor or 3-benzylidenenorcamphor and derivatives        thereof, e.g. 3-(4-methylbenzylidene)camphor;    -   4-aminobenzoic acid derivatives, preferably 2-ethylhexyl        4-(dimethylamino)benzoate, 2-octyl 4-(dimethylamino)benzoate and        amyl 4-(dimethylamino)benzoate;    -   esters of cinnamic acid, preferably 2-ethylhexyl        4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl        4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate        (octocrylene);    -   esters of salicylic acid, preferably 2-ethylhexyl salicylate,        4-isopropylbenzyl salicylate, homomenthyl salicylate;    -   derivatives of benzophenone, preferably        2-hydroxy-4-methoxybenzophenone,        2-hydroxy-4-methoxy-4′-methylbenzophenone,        2,2′-dihydroxy-4-methoxybenzophenone;    -   esters of benzalmalonic acid, preferably di-2-ethylhexyl        4-methoxybenzmalonate;    -   triazine derivatives, such as e.g.        2,4,6-trianilino(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine        and octyl triazone or dioctyl butamido triazone (Uvasorb® HEB);    -   propane-1,3-diones, such as e.g.        1-(4-tert-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dione;    -   ketotricyclo(5.2.1.0)decane derivatives.

Suitable water-soluble substances are:

-   -   2-phenylbenzimidazole-5-sulphonic acid and the alkali metal,        alkaline earth metal, ammonium, alkylammonium, alkanolammonium        and glucammonium salts thereof;    -   1H-benzimidazole-4,6-disulphonic acid, 2,2′-(1,4-phenylene)bis-,        disodium salt (Neo Heliopan® AP)    -   sulphonic acid derivatives of benzophenones, preferably        2-hydroxy-4-methoxybenzophenone-5-sulphonic acid and its salts;    -   sulphonic acid derivatives of 3-benzylidenecamphor, such as e.g.        4-(2-oxo-3-bornylidene methyl)benzene sulphonic acid and        2-methyl-5-(2-oxo-3-bornylidene)sulphonic acid and salts        thereof.

Suitable typical UV-A filters are in particular derivatives ofbenzoylmethane, such as for example1-(4′-tert-butylphenyl)-3-(4′-methoxyphenyl)propane-1,3-dione,4-tert-butyl-4′-methoxydibenzoylmethane (Parsol® 1789),2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid hexyl ester (Uvinul® APlus), 1-phenyl-3-(4′-isopropylphenyl)propane-1,3-dione, and enaminecompounds. The UV-A and UV-B filters can of course also be used inmixtures. Particularly favourable combinations consist of thederivatives of benzoylmethane, e.g.4-tert-butyl-4′-methoxydibenzoylmethane (Parsol® 1789) and 2-ethylhexyl2-cyano-3,3-phenylcinnamate (octocrylene) in combination with esters ofcinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate and/or propyl4-methoxycinnamate and/or isoamyl 4-methoxycinnamate. Such combinationsare advantageously combined with water-soluble filters such as e.g.2-phenylbenzimidazole-5-sulphonic acid and the alkali metal, alkalineearth metal, ammonium, alkylammonium, alkanolammonium and glucammoniumsalts thereof.

Besides the stated soluble substances, insoluble light protectionpigments, namely finely disperse metal oxides and salts are alsosuitable for this purpose. Examples of suitable metal oxides are inparticular zinc oxide and titanium dioxide and in addition oxides ofiron, zirconium, silicon, manganese, aluminium and cerium, and mixturesthereof. Salts that can be used are silicates (talc), barium sulphateand zinc stearate. The oxides and salts are used in the form of thepigments for skincare and skin-protecting emulsions and decorativecosmetics. The particles here should have an average diameter of lessthan 100 nm, preferably between 5 and 50 nm and in particular between 15and 30 nm. They can have a spherical shape, although it is also possibleto use those particles which have an ellipsoidal shape or a shape whichdeviates in some other way from the spherical configuration. Thepigments can also be present in surface-treated form, i.e.hydrophilicized or hydrophobicized. Typical examples are coated titaniumdioxides, such as e.g. titanium dioxide T 805 (Degussa) or Eusolex®T2000, Eusolex® T, Eusolex® T-ECO, Eusolex® T-S, Eusolex® T-Aqua,Eusolex® T-45D (all Merck), Uvinul TiO₂ (BASF). Suitable hydrophobiccoating agents here are in particular silicones and specificallytrialkoxyoctylsilanes or simethicones. In sun protection compositions,preference is given to using so-called micro- or nanopigments.Preference is given to using micronized zinc oxide such as e.g. Z-COTE®or Z-COTE HP1®.

Humectants

Humectants serve to further optimize the sensory properties of thecomposition and for regulating the moisture in the skin. At the sametime, the low-temperature stability of the preparations according to theinvention is increased, especially in the case of emulsions. Thehumectants are usually present in an amount of from 0.1 to 15% byweight, preferably 1 to 10% by weight, and in particular 5 to 10% byweight.

Of suitability according to the invention are, inter alia, amino acids,pyrrolidone carboxylic acid, lactic acid and salts thereof, lactitol,urea and urea derivatives, uric acid, glucosamine, creatinine, cleavageproducts of collagen, chitosan or chitosan salts/derivatives, and inparticular polyols and polyol derivatives (e.g. glycerol, diglycerol,triglycerol, ethylene glycol, propylene glycol, butylene glycol,erythritol, 1,2,6-hexanetriol, polyethylene glycols such as PEG-4,PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18,PEG-20), sugars and sugar derivatives (including fructose, glucose,maltose, maltitol, mannitol, inositol, sorbitol, sorbitylsilanediol,sucrose, trehalose, xylose, xylitol, glucuronic acid and salts thereof),ethoxylated sorbitol (sorbeth-6, sorbeth-20, sorbeth-30, sorbeth-40),honey and hydrogenated honey, hydrogenated starch hydrolysates, andmixtures of hydrogenated wheat protein and PEG-20 acetate copolymer.According to the invention, glycerol, diglycerol, triglycerol andbutylene glycol are preferably suitable as humectants.

Biogenic Active Ingredient and Antioxidants

Biogenic active ingredients are for example to be understood as meaningtocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid,(deoxy)ribonucleic acid and fragmentation products thereof, β-glucans,retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, aminoacids, ceramides, pseudoceramides, essential oils, plant extracts, suchas e.g. prune extract, bambaranut extract and vitamin complexes.

Antioxidants interrupt the photochemical reaction chain which istriggered when UV radiation penetrates into the skin. Typical examplesthereof are amino acids (e.g. glycine, histidine, tyrosine, tryptophan)and derivatives thereof, imidazoles (e.g. urocaninic acid) andderivatives thereof, peptides such as D,L-carnosine, D-carnosine,L-carnosine and derivatives thereof (e.g. anserine), carotenoides,carotenes (e.g. α-carotene, β-carotene, lycopene) and derivativesthereof, chlorogenic acid and derivatives thereof, lipoic acid andderivatives thereof (e.g. dihydrolipoic acid), aurothioglucose,propylthiouracil and other thiols (e.g. thioredoxin, glutathione,cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl,propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl,cholesteryl and glyceryl esters thereof), and salts thereof, dilaurylthiodipropionate, distearyl thiodipropionate, thiodipropionic acid andderivatives thereof (esters, ethers, peptides, lipids, nucleotides,nucleosides and salts), and sulphoximine compounds (e.g. buthioninesulphoximines, homocysteine sulphoximine, buthioninesulphones, penta-,hexa-, heptathionine sulphoximine) in very low tolerated doses (e.g.pmol to μmol/kg), also (metal) chelating agents (e.g. α-hydroxy fattyacids, palmitic acid, phytinic acid, lactoferrin), α-hydroxy acids (e.g.citric acid, lactic acid, malic acid), humic acid, bile acid, bileextracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof,unsaturated fatty acids and derivatives thereof (e.g. γ-linolenic acid,linoleic acid, oleic acid), folic acid and derivatives thereof,ubiquinone and ubiquinol and derivatives thereof, vitamin C andderivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbylacetate), tocopherols and derivatives (e.g. vitamin E acetate), vitaminA and derivatives (vitamin A palmitate), and coniferyl benzoate ofbenzoin resin, rutinic acid and derivatives thereof, α-glycosylrutin,ferrulic acid, furfurylideneglucitol, carnosine, butylhydroxytoluene,butylhydroxyanisole, nordihydroguaiacic acid, nordihydroguaiaretic acid,trihydroxybutyrophenone, uric acid and derivatives thereof, mannose andderivatives thereof, superoxide dismutase, zinc and derivatives thereof(e.g. ZnO, ZnSO₄) selenium and derivatives thereof (e.g.selenomethionine), stilbenes and derivatives thereof (e.g. stilbeneoxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers,sugars, nucleotides, nucleosides, peptides and lipids) of thesespecified active ingredients that are suitable according to theinvention.

Deodorants and Germicidal Agents

Cosmetic deodorants counteract, conceal or eliminate body odours. Bodyodours are formed as a result of the action of skin bacteria on apocrineperspiration, during which unpleasant-smelling degradation products areformed. Accordingly, deodorants comprise active ingredients whichfunction as germicidal agents, enzyme inhibitors, odour absorbers orodour concealers.

Germicidal agents. Suitable germicidal agents are in principle allsubstances effective against Gram-positive bacteria, such as e.g.4-hydroxybenzoic acid and its salts and esters,N-(4-chlorophenyl)-N″-(3,4-dichlorophenyl)urea,2,4,4″-trichloro-2″-hydroxydiphenyl ether (triclosan),4-chloro-3,5-dimethylphenol, 2,2′-methylenebis(6-bromo-4-chlorophenol),3-methyl-4-(1-methylethyl)phenol, 2-benzyl-4-chlorophenol,3-(4-chlorophenoxy)-1,2-propanediol, 3-iodo-2-propynyl butylcarbamate,chlorhexidine, 3,4,4′-trichlorocarbanilide (TTC), antibacterialfragrances, thymol, thyme oil, eugenol, clove oil, menthol, mint oil,farnesol, phenoxyethanol, glycerol monocaprinate, glycerolmonocaprylate, glycerol monolaurate (GML), diglycerol monocaprinate(DMC), salicylic acid N-alkylamides such as e.g. salicylic acidn-octylamide or salicylic acid n-decylamide.

Enzyme inhibitors. Suitable enzyme inhibitors are, for example, esteraseinhibitors. These are preferably trialkyl citrates such as trimethylcitrate, tripropyl citrate, triisopropyl citrate, tributyl citrate andin particular triethyl citrate (Hydagen® CAT). The substances inhibitthe enzyme activity and thereby reduce the odour formation. Furthersubstances which are contemplated as esterase inhibitors are sterolsulphates or phosphates, such as, for example, lanosterol, cholesterol,campesterol, stigmasterol and sitosterol sulphates or phosphates,dicarboxylic acids and esters thereof, such as, for example, glutaricacid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipicacid, adipic acid monoethyl ester, adipic acid diethyl ester, malonicacid and malonic acid diethyl ester, hydroxycarboxylic acids and estersthereof, such as, for example, citric acid, malic acid, tartaric acid ortartaric acid diethyl ester, and also zinc glycinate.

Odour absorbers. Substances suitable as odour absorbers are those whichare able to absorb and largely retain odour-forming compounds. Theyreduce the partial pressure of the individual components and thus alsoreduce their spreading rate. It is important here that perfumes mustremain unaffected. Odour absorbers have no effectiveness towardsbacteria. They contain for example as the main constituent a complexzinc salt of ricinoleic acid or specific, largely odour-neutralfragrances, which are known to the person skilled in the art as“fixatives”, such as e.g. extracts of labdanum or styrax or certainabietic acid derivatives. Functioning as odour concealers are fragrancesor perfume oils which, in addition to their function as odourconcealers, impart their particular scent note to the deodorants.Perfume oils that may be mentioned are, for example, mixtures of naturaland synthetic fragrances. Natural fragrances are extracts from flowers,stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses,needles and branches, and resins and balsams. Also of suitability areanimal raw materials, such as, for example, civet and castoreum. Typicalsynthetic fragrance compounds are products of the ester, ether,aldehyde, ketone, alcohol and hydrocarbon types. Fragrance compounds ofthe ester type are e.g. benzyl acetate, p-tert-butyl cyclohexylacetate,linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate,allyl cyclohexylpropionate, styrallyl propionate and benzyl salicylate.The ethers include, for example, benzyl ethyl ether, the aldehydesinclude e.g. the linear alkanals having 8 to 18 carbon atoms, citral,citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde,hydroxycitronellal, lilial and bourgeonal; the ketones include e.g. theionones and methyl cedryl ketone; the alcohols include anethol,citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethylalcohol and terpineol; the hydrocarbons include primarily the terpenesand balsams. However, preference is given to using mixtures of differentfragrances which together produce a pleasant scent note. Essential oilsof lower volatility, which are mostly used as aroma components, are alsosuitable as perfume oils, e.g. sage oil, camomile oil, clove oil,melissa oil, mint oil, cinnamon leaf oil, linden blossom oil, juniperberry oil, vetiver oil, olibanum oil, galbanum oil, labdanum oil andlavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral,citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol,benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan,indole, hedione, sandelice, lemon oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal, lavandin oil, clary sage oil, β-damascone,geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur,Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid,geranyl acetate, benzyl acetate, rose oxide, romilat, irotyl andfloramat alone or in mixtures, are used.

Antiperspirants. Antiperspirants reduce the formation of perspiration byinfluencing the activity of the eccrine sweat glands, and thuscounteract armpit wetness and body odour. Aqueous or anhydrousformulations of antiperspirants typically comprise the followingingredients:

-   -   astringent active ingredients,    -   oil components,    -   nonionic emulsifiers,    -   coemulsifiers,    -   consistency regulators,    -   auxiliaries such as e.g. thickeners or complexing agents and/or    -   nonaqueous solvents such as e.g. ethanol, propylene glycol        and/or glycerol.

Suitable astringent antiperspirant active ingredients are in particularsalts of aluminium, zirconium or zinc. Such suitable antihydroticallyeffective substances are e.g. aluminium chloride, aluminiumchlorohydrate, aluminium dichlorohydrate, aluminium sesquichlorohydrateand complex compounds thereof e.g. with propylene glycol-1,2. Aluminiumhydroxyallantoinate, aluminium chloride tartrate, aluminium zirconiumtrichlorohydrate, aluminium zirconium tetrachlorohydrate, aluminiumzirconium pentachlorohydrate and complex compounds thereof e.g. withamino acids such as glycine. In addition, oil-soluble and water-solubleauxiliaries customary in antiperspirants may be present in relativelysmall amounts. Such oil-soluble auxiliaries can be for example:

-   -   antiflammatory, skin-protecting or nice-smelling essential oils,    -   synthetic skin-protecting active ingredients and/or    -   oil-soluble perfume oils.

Customary water-soluble additives are e.g. preservatives, water-solublefragrances, pH regulators, e.g. buffer mixtures, water-solublethickeners, e.g. water-soluble natural or synthetic polymers such ase.g. xanthan gum, hydroxyethyl cellulose, polyvinylpyrrolidone or highmolecular weight polyethylene oxides.

Film Formers

Customary film formers are, for example, chitosan, microcrystallinechitosan, quaternized chitosan, polyvinylpyrrolidone,vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acidseries, quaternary cellulose derivatives, collagen, hyaluronic acid andsalts thereof, and similar compounds.

Antidandruff Active Ingredients

Suitable antidandruff active ingredients are piroctone olamine(1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-(1H)-pyridinonemonoethanolamine salt), Baypival® (climbazole), Ketoconazol®,(4-acetyl-1-{-4-[2-(2,4-dichlorophenyl)r-2-(1H-imidazol-1-ylmethyl)-1,3-dioxylan-c-4-ylmethoxyphenyl}piperazine,ketoconazole, elubiol, selenium disulphide, sulphur colloidal, sulphurpolyethylene glycol sorbitan monooleate, sulphur ricinol polyethoxylate,sulphur tar distillates, salicylic acid (or in combination withhexachlorophene), undecylenic acid monoethanolamide sulphosuccinate Nasalt, Lamepon® UD (protein-undecylenic acid condensate), zincpyrithione, aluminium pyrithione and magnesium pyrithione/dipyrithionemagnesium sulphate.

Swelling Agents

Swelling agents used for aqueous phases can be montmorillonites, claymineral substances, pemulen, and alkyl-modified carbopol grades(Goodrich). Further suitable polymers and swelling agents can be foundin the overview by R. Lochhead in Cosm. Toil. 108, 95 (1993).

Insect Repellents

Suitable insect repellents are N,N-diethyl-m-toluamide, 1,2-pentanediolor ethyl butylacetylaminopropionate. A suitable self-tanning agent isdihydroxyacetone. Suitable as tyrosine inhibitors, which prevent theformation of melanine and are used in depigmentation compositions, are,for example, arbutin, ferrulic acid, kojic acid, coumaric acid andascorbic acid (vitamin C).

Ingredients for Oral and Dental Care Compositions

Toothpastes or dental creams are generally understood as being gel-likeor pasty preparations made of water, thickeners, humectants, abrasive orpolishing bodies, surfactants, sweeteners, aroma substances, deodorizingactive ingredients and active ingredients to combat oral and dentaldiseases. In the toothpastes according to the invention it is possibleto use all customary cleaning bodies, such as e.g. chalk, dicalciumphosphate, insoluble sodium metaphosphate, aluminium silicates, calciumpyrophosphate, finely divided synthetic resins, silicas, aluminium oxideand aluminium oxide trihydrate.

Preferably suitable cleaning bodies for the toothpastes according to theinvention are in particular finely divided xerogel silicas, hydrogelsilicas, precipitated silicas, aluminium oxide trihydrate and finelydivided alpha-aluminium oxide or mixtures of these cleaning bodies inamounts of from 15 to 40% by weight of the toothpaste. Suitablehumectants are predominantly low molecular weight polyethylene glycols,glycerol, sorbitol or mixtures of these products in amounts up to 50% byweight. Among the known thickeners, the thickening, finely divided gelsilicas and hydrocolloids, such as e.g. carboxymethylcellulose,hydroxyethylcellulose, hydroxypropylguar, hydroxyethyl starch,polyvinylpyrrolidone, high molecular weight polyethylene glycol, plantgums such as tragacanth, agar agar, carrageen moss, gum arabic, xanthamgum and carboxyvinyl polymers (e.g. Carbopol® grades) are suitable. Inaddition to the mixtures of menthofuran and menthol compounds, the oraland dentalcare compositions can comprise in particular surface-activesubstances, preferably anionic and nonionic high-foam surfactants, suchas the substances already specified above, but in particular alkyl ethersulphate salts, alkyl polyglucosides and mixtures thereof.

Further customary toothpaste additives are:

-   -   preservatives and antimicrobial substances such as e.g.        p-hydroxybenzoic acid methyl, ethyl or propyl ester, sodium        sorbate, sodium benzoate, bromochlorophene, phenyl salicylic        acid ester, thymol and the like;    -   anti-tartar active ingredients, e.g. organophosphates such as        1-hydroxyethane-1,1-diphosphonic acid,        1-phosphonopropane-1,2,3-tricarboxylic acid and others which are        known e.g. from U.S. Pat. No. 3,488,419, DE 2224430 A1 and DE        2343196 A1;    -   other caries-inhibiting substances such as e.g. sodium fluoride,        sodium monofluorophosphate, tin fluoride;    -   sweeteners, such as e.g. saccharin sodium, sodium cyclamate,        sucrose, lactose, maltose, fructose or Apartam®,        (L-aspartyl-L-phenylalanine methyl ester), stevia extracts or        sweetening constituents thereof, in particular rebaudioside;    -   additional aromas such as e.g. eucalyptus oil, anise oil, fennel        oil, caraway oil, methyl acetate, cinnamaldehyde, anethole,        vanillin, thymol, and mixtures of these and other natural and        synthetic aromas;    -   pigments such as e.g. titanium dioxide;    -   dyes;    -   buffer substances such as e.g. primary, secondary or tertiary        alkali metal phosphates or citric acid/sodium citrate;    -   wound-healing and inflammatory substances such as e.g.        allantoin, urea, azulene, chamomile active ingredients and        acetyl salicylic acid derivatives.

A preferred embodiment of the cosmetic preparations is toothpastes inthe form of an aqueous, pasty dispersion, comprising polishing agents,humectants, viscosity regulators and optionally further customarycomponents, and also the mixture of menthofuran and menthol compounds inamounts of from 0.5 to 2% by weight.

In mouthwashes, a combination with aqueous-alcoholic solutions ofvarying concentration gradient of essential oils, emulsifiers,astringent and toning drug extracts, tartar-inhibiting, antibacterialadditives and taste correctors is directly possible. A further preferredembodiment of the invention is a mouthwash in the form of an aqueous oraqueous-alcoholic solution comprising the mixture of menthofuran andmenthol compounds in amounts of from 0.5 to 2% by weight. In mouthwasheswhich are diluted prior to use, adequate effects can be attained usinghigher concentrations corresponding to the intended dilution ratio.

Hydrotropes

To improve the flow behaviour, hydrotropes, such as, for exampleethanol, isopropyl alcohol, or polyols can also be used; thesesubstances largely correspond to the carriers described at the start.Polyols that are contemplated here have preferably 2 to 15 carbon atomsand at least two hydroxyl groups. The polyols can also contain furtherfunctional groups, in particular amino groups, and/or be modified withnitrogen. Typical examples are

-   -   glycerol;    -   alkylene glycols, such as, for example, ethylene glycol,        diethylene glycol, propylene glycol, butylene glycol, hexylene        glycol, and polyethylene glycols with an average molecular        weight of from 100 to 1000 Daltons;    -   technical oligoglycerol mixtures with a degree of        self-condensation of from 1.5 to 10, such as for example        technical-grade diglycerol mixtures with a diglycerol content of        from 40 to 50% by weight;    -   methylol compounds, such as in particular trimethylolethane,        trimethylolpropane, trimethylolbutane, pentaerythritol and        dipentaerythritol;    -   low alkyl glucosides, in particular those having 1 to 8 carbon        atoms in the alkyl radical, such as, for example, methyl- and        butylglucoside;    -   sugar alcohols having 5 to 12 carbon atoms, such as, for        example, sorbitol or mannitol,    -   sugars having 5 to 12 carbon atoms, such as, for example,        glucose or sucrose;    -   amino sugars, such as, for example, glucamine;    -   dialcoholamines, such as diethanolamine or        2-amino-1,3-propanediol.

Preservatives

Suitable preservatives are, for example, phenoxyethanol, formaldehydesolution, parabens, pentanediol or sorbic acid, as well as the silvercomplexes known under the name Surfacine® and the other classes ofsubstance listed in Annex 6, part A and B of the Cosmetics Ordinance.

Perfume Oils and Aromas

Perfume oils that may be mentioned are mixtures of natural and syntheticfragrances. Natural fragrances are extracts of flowers (lily, lavender,rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium,patchouli, petitgrain), fruits (anise, coriander, caraway, juniper),fruit peels (bergamot, lemon, orange), roots (mace, angelica, celery,cardamom, costus, iris, calmus), woods (pinewood, sandalwood, guaiacwood, cedarwood, rosewood), herbs and grasses (tarragon, lemon grass,sage, thyme), needles and branches (spruce, fir, pine, dwarf-pine),resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum,opoponax). Also of suitability are animal raw materials such as, forexample, civet and castoreum. Typical synthetic fragrance compounds areproducts of the ester, ether, aldehyde, ketone, alcohol and hydrocarbontypes. Fragrance compounds of the ester type are e.g. benzyl acetate,phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalylacetate, dimethylbenzyl carbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexylpropionate, styrallyl propionate and benzyl salicylate. Theethers include, for example, benzyl ethyl ether; the aldehydes includee.g. the linear alkanals having 8 to 18 carbon atoms, citral,citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde,hydroxycitronellal, lilial and bourgeonal; the ketones include e.g. theionones, α-isomethylionone and methyl cedryl ketone; the alcoholsinclude anethole, citronellol, eugenol, isoeugenol, geraniol, linalool,phenylethyl alcohol and terpineol; the hydrocarbons include primarilythe terpenes and balsams. However, preference is given to using mixturesof different fragrances which together produce a pleasant scent note.Essential oils of lower volatility, which are mostly used as aromacomponents, are also suitable as perfume oils, e.g. sage oil, chamomileoil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden blossomoil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil,labolanum oil and lavandin oil. Preference is given to using bergamotoil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol,α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde,linalool, Boisambrene Forte, ambroxan, indole, hedione, sandelice, lemonoil, mandarin oil, orange oil, allyl amylglycolate, cyclovertal,lavandin oil, clary sage oil, β-damascone, geranium oil bourbon,cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP,evernyl, iraldein gamma, phenyl acetic acid, geranyl acetate, benzylacetate, rose oxide, romillat, irotyl and floramat, alone or inmixtures.

Suitable aromas are, for example, peppermint oil, spearmint oil, aniseedoil, star anise oil, caraway oil, eucalyptus oil, fennel oil, lemon oil,wintergreen oil, clove oil, menthol and the like.

Dyes

Dyes which can be used are the substances approved and suitable forcosmetic purposes, as are listed for example in the publication“Kosmetische Färbemittel [Cosmetic Colorants]” of theFarbstoffkommission der Deutschen Forschungsgemeinschaft [DyesCommission of the German Research Society], Verlag Chemie, Weinheim,1984, pp. 81-106. Examples are cochenille red A (C.I.16255), patent blueV (C.I.42051), indigotin (C.I.73015), chlorophyllin (C.I.75810),quinoline yellow (C.I.47005), titanium dioxide (C.I.77891), indanthreneblue RS (C.I.69800) and madder lake (C.I.58000). Luminol may also bepresent as luminescence dye. These dyes are usually used inconcentrations of from 0.001 to 0.1% by weight, based on the totalmixture.

The total fraction of auxiliaries and additives can be 1 to 50,preferably 5 to 40, % by weight—based on the compositions. Thecompositions can be produced by customary cold or hot processes;preference is given to working in accordance with the phase inversiontemperature method.

Mixtures

A further subject matter of the invention relates to a first mixture ofat least four lactones selected from the group consisting ofγ-hexalactone, γ-heptalactone, γ-octalactone, γ-nonalactone,γ-decalactone, γ-undecalactone, γ-dodecalactone, δ-hexalactone,δ-heptalactone, δ-octalactone, δ-nonalactone, δ-decalactone,δ-undecalactone, δ-dodecalactone.

This is because it has been proven that the best odiferous improvementscan be attained if more than one of the lactones to be used according tothe invention, preferably two and in particular three or four lactones,are used together, where the weight ratio should be approximatelybalanced.

In a first preferred embodiment of the invention, either only γ-lactonesor only δ-lactones are used. In a second, the lactone mixtures to beused in each case comprise γ- and δ-lactones of identical chain length.Particularly preferred mixtures comprise in each case γ-decalactone andγ-undecalactone.

The mixtures can be added to the end products in the amounts alreadystated, e.g. 0.01 to 1% by weight, in particular 0.02 to 0.5% by weightand particularly preferably 0.05 to 0.1% by weight—based on thepreparations.

A further subject matter of the invention is directed to a secondmixture comprising

-   (a) at least two representatives of the group which is formed by    nonalactone, decalactone and undecalactone, and also-   (b) aldehydes of the formula (II)    R²COH  (II)    -   in which R² is a linear or branched, saturated or unsaturated        alkyl and/or alkenyl radical having 6 to 22 carbon atoms.

Preferably, the mixtures according to the invention comprise, ascomponent (a), gamma-lactones and, as component (b) unsaturatedaldehydes which are preferably present in trans-conformation and inparticular have 8 to 12 carbon atoms. The mixtures comprise thecomponents (a) and (b) preferably in quantitative ratios of from1:0.00001 to 1:120, preferably 1:0.001 to 1:50, in particular 1:0.01 to1:10 and particularly preferably 1:0.1 to 1:1.

The mixtures according to the invention are characterized in that theyare characterized by an intense milky-creamy odour whereas the lactonesper se are virtually odour-less and the aldehydes have a pungent, greasyand extremely unpleasant odour.

EXAMPLES Examples 1 and 2, Comparative Example C1

A commercially available soap base (Soap Base VVF, Henkel Poland) wasadmixed with in each case 0.05% by weight of a mixture (a) ofγ-decalactone and γ-undecalactone (weight ratio 1:1) and (b)γ-nonalactone, γ-decalactone, δ-decalactone and γ-undecalactone (weightratio 1:1:1:1) and the odour sensorics by a panel consisting of 5.Intensity scale from 1 to 25. The results are summarized in Table 1.Examples 1 and 2 are in accordance with the invention, example C1 servesfor comparison.

TABLE 1 Sensory assessment of a soap base Odour note C1 1 2 Positiveodour notes sweet 1 17 18 creamy 4 13 12 floral 1 2 2 aromatic 2 1 1Negative odour notes greasy 4 1 1 oxidized 11 2 2 chemical 2 2 2 musty 11 1

The examples and the comparative example show that by adding even smallamounts of lactones not only are the negative odour notes of the soapmixture masked, but instead pleasant odour notes come to the fore.

Formulation examples for various laundry detergents, dishwashingdetergents and cleaners which comprise the lactones to be used accordingto the invention are given below. As the product NeoScent AA, a mixtureof γ-nonalactone, γ-decalactone, δ-decalactone and γ-undecalactone(weight ratio 1:1:1:1) is used. All quantitative amounts are % byweight.

TABLE 2 Bar soaps Composition A1 A2 A3 Sodium C12/14 Olefin Sulphonate40.0 — — Disodium Lauryl Sulphosuccinate — 40.0 — Lauryl Glucoside 15.015.0 55.0 Cetylstearyl Alcohol 12.0 12.0 12.0 Paraffin Oil (m.p. 54 to56° C.) 8.0 8.0 8.0 Maize Starch, degraded 8.0 8.0 8.0 Palmitic Acid(and) Stearic Acid 5.5 5.5 5.5 Glyceryl Stearate 2.0 2.0 2.0 CocoGlyceride 2.0 2.0 2.0 Polyquaternium-7 1.0 1.0 1.0 Perfume oil 1.0 1.01.0 Titanium dioxide 0.5 0.5 0.5 NeoScent AA 0.05 0.05 0.05 Water ad 100

TABLE 3 Syndet soaps Composition B1 B2 B3 Lauryl Glucoside 15.0 15.015.0 Sodium C12/14 Olefin Sulphonate 40.0 40.0 — Sodium Lauryl Sulphate— — 40.0 Paraffin Oil (m.p. 54° C.) 8.0 8.0 8.0 Tallow Fatty Alcohol 7.07.0 7.0 Maize starch 17.0 — 17.0 Dextrose — 17.0 — Coco Fatty Acids 10.010.0 10.0 Titanium dioxide 1.0 1.0 1.0 Perfume oil 1.0 1.0 1.0 NeoScentAA 0.05 0.05 0.05 Water ad 100

TABLE 4 WC gel toilet blocks Composition C1 C2 C3 C4 C5 C6 LaurylGlucoside 5.0 1.5 1.5 1.5 5.0 1.5 Decyl Glucoside — 3.5 3.5 3.5 — 3.5Sodium Lauryl Sulphate 9.0 6.0 3.0 — 9.0 6.0 Sodium Laureth Sulphate —3.0 — — — 3.0 Cocamidopropyl Betaine — — 6.0 9.0 — — Ethanol 3.5 3.5 3.53.5 3.5 3.5 Citric Acid Mono Hydrate 3.6 3.6 3.6 3.6 3.6 3.6 SodiumHydroxide 0.5 0.5 0.5 0.5 0.5 0.5 Laurylamine + 1EO 4.5 3.0 5.0 2.5 — —Hexanediol-1,6 — 0.5 — 0.5 — Perfume oil 0.5 0.5 0.5 0.5 0.5 0.5NeoScent AA  0.05  0.05  0.05  0.05  0.05  0.05 Water ad 100

TABLE 5 Bleach solutions Composition D1 D2 D3 D4 D5 Sodium hypochlorite4.0 4.0 4.0 4.0 4.0 Sodium hydroxide 0.9 0.9 0.9 0.9 0.9 SodiumLaureth-2 Sulphate — 2.0 2.0 — 2.0 Lauryldimethylamine oxide — 2.0 — —2.0 Coco Glucosides — — 0.5 — — Laureth-2 — — 1.0 — — Sodium silicate 0.95  0.95  0.95  0.95  0.95 Sodium carbonate — — — — — Amine oxidephosphonic acid 0.1 0.1 0.1 0.1 0.1 Polyacrylate 1.0 1.0 1.0 1.0 1.0Perfume oil 0.5 0.5 0.5 0.5 0.5 NeoScent AA  0.05  0.05  0.05  0.05 0.05 Water ad 100

TABLE 6 Powder detergents Composition E1 E2 E3 E4 E5 E6 Sodium Laureth-1Sulphate 12.0  8.0 8.0 4.0 4.0 — Dodecylbenzene sulphonate — — 4.0 8.04.0 8.0 Sodium Lauryl Sulphate — 4.0 — — 4.0 4.0 Coco Fatty Acid, SodiumSalt 1.0 1.0 1.0 1.0 1.0 1.0 Coco Glucosides — — — 7.0 — — Laureth-5 7.07.0 7.0 — 7.0 7.0 Zeolite A 24.0  24.0  24.0  24.0  24.0  24.0  Sodiumsilicate, amorphous 3.0 3.0 3.0 3.0 3.0 3.0 (modulus 1:2) Sodiumcarbonate 12.0  12.0  12.0  12.0  12.0  12.0  Polymeric polycarboxylate5.5 5.5 5.5 5.5 5.5 5.5 Perborate monohydrate 16.0  16.0  16.0  16.0 16.0  16.0  Tetraacetylethylenediamine 5.5 5.5 5.5 5.5 5.5 5.5Carboxymethylcellulose 0.3 0.3 0.3 0.3 0.3 0.3 Optical brightener 0.20.2 0.2 0.2 0.2 0.2 Enzyme granules (protease) 1.0 1.0 1.0 1.0 1.0 1.0Perfume oil 0.5 0.5 0.5 0.5 0.5 0.5 NeoScent AA  0.05  0.05  0.05  0.05 0.05  0.05 Water ad 100

TABLE 7 Hand dishwashing detergent Composition F1 F2 F3 F4 SodiumLaureth-1 Sulphate 15 15 15 15 Sodium Laureth-2 Sulphate 15 — — — SodiumLauryl Sulphate — 15 — — Coco Glucosides — — 15 — Sodium OctylSulphosuccinate — — 15 Cocamidopropyl Betaine 1 3 3 3 Perfume oil 0.50.5 0.5 0.5 NeoScent AA 0.05 0.05 0.05 0.05 Water ad 100

TABLE 8 Cleaner Composition G1 G2 G3 G4 G5 G6 C_(12/16)-Alkyl sulphateNa salt 5.0 5.0 4.0 0 5.0 0 C_(16/18)-Tallow fatty alcohol + 3.0 3.0 4.00 0 5.0 25EO C_(12/14)-Cocoalkyl 1.0 2.0 2.0 5.0 0 0 oligoglucosideSodium metasilicate 15.0 15.0 15.0 15.0 15.0 15.0 Sodium carbonate 26.024.0 24.0 30.0 30.0 30.0 Sulphonated styrene/MSA — 2.0 2.0 — — —copolymer, sodium salt Limonene 0.1 0.1 0.1 0.1 0.1 0.1 NeoScent AA 0.050.05 0.05 0.05 0.05 0.05 Sodium tripolyphosphate ad 100

TABLE 9 Cosmetic cream Composition H1 H2 H3 H4 H5 Glyceryl Stearate(and) Ceteareth 5.0 5.0 4.0 — — 12/20 (and) Cetearyl Alcohol (and) CetylPalmitate Ceteareth-12 — — 1.0 — — Polyglyceryl-3 Isostearate — — — 4.0— Polyglyceryl-2 Dipolyhydroxystearate — — — — 4.0 Glyceryl Oleate — — —2.0 — PEG-7 Glyceryl Cocoate — — — — 2.0 Dicaprylyl Ether — — — 5.0 6.0Hexyldecanol (and) Hexyldecyl — — 3.0 10.0  9.0 Laurate CetearylIsononanoate 3.0 3.0 — — — Decyl Oleate 3.0 3.0 — — — Coco CaprylateCaprate — — 3.0 5.0 5.0 Beeswax — — — 7.0 5.0 Hydrolyzed Elastin 2.0 — —— — Hydrolyzed Collagen — 2.0 — — — Hydrolyzed Wheat Gluten — — 0.5 — —Sodium Cocoyl Hydrolyzed Wheat — — — 0.5 0.5 Protein Glycol Distearate(and) Laureth-4 5.0 5.0 4.0 — — (and) Cocamidopropyl Betaine Glycerin(86% strength by weight) — — 1.0 — — Perfume oil 0.5 0.5 0.5 0.5 0.5NeoScent AA  0.05  0.05  0.05  0.05  0.05 Water ad 100

The invention claimed is:
 1. A method for masking an odoriferousincorrect note in an oleochemical composition comprising: adding to saidcomposition a mixture of at least two lactones comprising: (a)γ-decalactone and (b) γ-undecalactone in an amount of from about 0.01 to0.1 wt-% based on the weight of the composition, and wherein saidcomposition is selected from the group consisting of a soap base, alaundry detergent, a dishwashing detergent, a hard surface cleaner, anda cosmetic preparation wherein the cosmetic preparation is a cosmeticselected from the group consisting of a cosmetic cream and/or a cosmeticcontaining an additive selected from the group consisting of a UV lightprotection factor, an antiperspirant, an antidandruff agent, an insectrepellent, a self-tanning agent, and a depigmentation agent, whereinsaid composition prior to the addition of said lactones has a greasy ora rancid odour note.
 2. The method of claim 1, wherein said compositioncomprises a component causing said incorrect note selected from thegroup consisting of a free fatty acid, an aldehyde, and an oxidationproduct of a fat or oil.
 3. The method of claim 1 wherein said mixtureof at least two lactones further comprising at least one additionallactone selected from the group consisting of γ-hexalactone,γ-heptalactone, γ-octalactone, γ-nonalactone, γ-dodecalactone,δ-hexalactone, δ-heptalactone, δ-octalactone, δ-nonalactone,δ-decalactone, δ-undecalactone, δ-dodecalactone, and mixtures thereof.4. The method of claim 1, wherein said mixture of at least two lactonesconsists of: (a) γ-decalactone; (b) γ-undecalactone; (c) γ-nonalactone;and (d) δ-decalactone.